TWI404773B - New dry mineral pigment containing calcium carbonate, aqueous suspension containing it and its uses - Google Patents

Abstract

The invention concerns a process for manufacturing a dry mineral pigment containing a product formed in situ by the multiple reaction between a calcium carbonate and the product or products of reaction of the said carbonate with one or more moderately strong to strong H30+ ion donators and the product or products of reaction of the said carbonate with gaseous CO<SUB>2 </SUB>formed in situ and/or originating from an external supply and one or more compounds of formula R-X together with the mineral pigment obtained by the process, and its applications in the field of paint and/or plastics.

Description

Novel calcium carbonate-containing dry inorganic pigment, aqueous suspension containing the same and use thereof

The present invention relates to the technical field of inorganic fillers and in particular to an inorganic pigment for use in paints and/or plastics and/or coatings and/or mastics, which comprises calcium carbonate and the following a dry product formed in situ by multiple reactions: one or more medium-strength to strong H ₃ O ⁺ ion donor reaction products or multiple reaction products, and the carbonate and in situ formation and/or origin An externally supplied gaseous CO ₂ reaction product or a plurality of reaction products, and one or more compounds of the formula R-X, which are especially useful as a stream which allows viscosity to be controlled while maintaining the firmness of the polymer material. Variable conditioning fillers, and more particularly in the automotive industry, as a protective covering for underbody.

The present invention also relates to a method of producing a dry inorganic pigment and an inorganic pigment obtained by the method, the dry inorganic pigment comprising a product formed in situ by a multiple reaction between calcium carbonate and the following: the carbonate and a carbonate Or a reaction product or a plurality of reaction products of a medium strength to strong H ₃ O ⁺ ion donor, and a reaction product or a plurality of reactions of the carbonate and in situ formation and/or from externally supplied gaseous CO ₂ a product, and one or more compounds of formula R-X.

The dry inorganic pigment according to the present invention may be placed in an aqueous suspension by an anionic electrolyte prior to drying to obtain an anionic aqueous suspension of the filler containing a plurality of calcium carbonate and the following a product formed in situ by the reaction: a reaction product or a plurality of reaction products of the carbonate and one or more medium strength to strong H ₃ O ⁺ ion donors, and the carbonate and in situ formation and/or origin A reaction product or a plurality of reaction products of gaseous CO ₂ supplied externally, and one or more compounds of the formula R-X.

The anionic aqueous suspension and its corresponding product after drying may contain one or more anionic electrolytes such as, for example, one or more dispersing agents.

The dry inorganic pigment according to the present invention may be placed in an aqueous suspension by a cationic electrolyte prior to drying to obtain a cationic aqueous suspension of the filler containing a plurality of calcium carbonate and the following a product formed in situ by the reaction: a reaction product or a plurality of reaction products of the carbonate and one or more medium strength to strong H ₃ O ⁺ ion donors, and the carbonate and in situ formation and/or origin A reaction product or a plurality of reaction products of gaseous CO ₂ supplied externally, and one or more compounds of the formula R-X.

The cationic aqueous suspension and its corresponding product after drying may contain one or more cationic electrolytes such as, for example, one or more dispersing agents.

The dry inorganic pigment according to the present invention may be placed in an aqueous suspension by a weak anionic electrolyte prior to drying to obtain a weak anionic aqueous suspension of the filler, the filler containing a calcium carbonate and the following a product formed in situ by the multiplex reaction: a reaction product or a plurality of reaction products of the carbonate and one or more medium strength to strong H ₃ O ⁺ ion donors, and the carbonate and in situ formation and/or Or a reaction product or a plurality of reaction products derived from externally supplied gaseous CO ₂ , and one or more compounds of the formula R-X.

The weak anionic aqueous suspension and its corresponding product after drying may contain one or more weak anionic electrolytes such as, for example, one or more dispersing agents.

The invention also relates to the use of the dry inorganic pigment and the aqueous suspension of the inorganic pigment in the field of paints and/or plastics and/or coatings and/or thick coatings, in particular as a conditioning plastisol formulation and hard polychlorinated A rheological filler of the ethylene (PVC) type formulation and especially as a filler that allows viscosity to be controlled while maintaining the firmness of the plastisol formulation and the rigid PVC formulation, particularly for the door panel of the automotive industry. Protective covering material.

The invention also relates to a plastisol formulation containing the dry inorganic pigment and a rigid PVC formulation and a underbody protective covering.

Finally, the invention relates to paints and/or coatings and/or high build coatings containing the dry inorganic pigments.

Those skilled in the art - and thus attempting to control the rheology of the formulation used in the manufacture of the automobile body while maintaining the firmness of the polymer constituting the body, are well known in the patent application WO 00/20336, which provides familiarity with the art. A solution by picking the particle size of the filler used, but this solution is not fully satisfactory to those skilled in the art.

Those skilled in the art are also familiar with EP 377 149, and the solution used to improve rheology is not satisfactory.

FR 2 407 216 is also known to those skilled in the art, and the application proposes an agent intended to modify the rheological properties of a plastisol, which is composed of phosphoric anhydride or polyphosphoric acid and an organic derivative having at least one hydroxyl group. A phosphate derivative composed of an excess ester neutralized product obtained by the esterification reaction.

However, all of these documents do not allow the skilled person to maintain the firmness of the polymer constituting the body while controlling the rheology of the formulation used in the manufacture of the automobile body.

The Applicant continued his research in order to maintain the firmness of the car body while controlling the rheology of the formulation used in the car body. The applicant unexpectedly discovered a dry inorganic pigment containing a a product formed in situ by a multiple reaction between calcium carbonate and the following: a reaction product or a plurality of reaction products of the carbonate and one or more medium strength to strong H ₃ O ⁺ ion donors, and the carbonate and a reaction product or a plurality of reaction products formed in situ and/or derived from externally supplied gaseous CO ₂ , and one or more compounds of the formula R-X capable of rheologically forming in a plastisol formulation The plastisol weight is adjusted during this period and the weight gain is maintained while maintaining firmness.

The applicant has also developed a formula for obtaining a dry inorganic pigment (which contains a product of the reaction between the calcium carbonate and multiplex the carbonates formed in situ with the following: one or more moderate to strong H ₃ a reaction product or a plurality of reaction products of an O ⁺ ion donor, and a reaction product or a plurality of reaction products of the carbonate and in situ formed and/or derived from externally supplied gaseous CO ₂ , and one or more chemical formulas R A method of -X compound) which enables the underbody to obtain the above results and/or to obtain an aqueous coating having excellent corrosion resistance.

One object of the present invention is therefore a dry inorganic pigment comprising a product formed in situ from a multiple reaction between calcium carbonate and the carbonate and the following: one or more medium to strong H ₃ O ⁺ a reaction product or a plurality of reaction products of an ion donor, and a reaction product or a plurality of reaction products of the carbonate and in situ formed and/or derived from externally supplied gaseous CO ₂ , and one or more chemical formulas R-X compound of.

Another object of the invention is also a method of making the dry pigment.

Another object of the invention relates to an aqueous suspension of the inorganic pigment according to the invention.

Another object of the invention is the use of the dry inorganic pigment obtained by the process according to the invention and its use in the field of paints and/or plastics and/or coatings and/or high-paste coatings, in particular as a conditioning A plastisol formulation and a rheological filler of a rigid polyvinyl chloride (PVC) formulation and in particular as a filler that maintains viscosity while maintaining the firmness of the polymers.

More particularly, another object of the invention is the use of the dry inorganic pigment and the aqueous suspension of the inorganic pigment in the field of paints and/or plastics and/or coatings and/or high build coatings, in particular as a conditioning increase A plastisol formulation with a rheological filler of a rigid polyvinyl chloride (PVC) formulation and especially as a filler that maintains viscosity while maintaining the firmness of the plastisol formulation and the rigid PVC formulation, and especially for automotive applications The protective coating of the door under the door.

Furthermore, another object of the invention is a plastisol or rigid PVC formulation containing the inorganic pigment according to the invention.

Finally, another object of the invention is a paint and/or high build coating and/or coating formulation containing the inorganic pigment according to the invention.

Thus, the dry inorganic product according to the present invention is characterized in that it contains a product formed in situ by a multiple reaction between calcium carbonate and the following: the carbonate and one or more medium strength to strong H3O+ ion donors a reaction product or a plurality of reaction products, and a reaction product or a plurality of reaction products of the carbonate and in situ formed and/or derived from externally supplied gaseous CO ₂ , and one or more compounds of the formula R-X.

In particular, the dry inorganic pigment according to the invention is characterized in that the R group of the compound of formula R-X represents a carbon-containing group, whether or not saturated, having from 8 to 24 carbon atoms, such as a straight chain or Branched alkyl, alkaryl, aralkyl, aryl, polyaryl or cyclic group or mixtures thereof, and in the X group of the compound of formula R-X or of a plurality of compounds It represents a group such as a carboxylic acid group, an amine group, a hydroxyl group, a phosphonic acid group or a mixture thereof.

Still more particularly, the compound of formula R-X is selected from fatty acids, aliphatic amines or aliphatic alcohols, preferably having from 8 to 24 carbon atoms, such as stearic acid, oleic acid, whether saturated or not. , linoleic acid, myristic acid, octanoic acid or a mixture of such lipids, preferably having from 16 to 18 carbon atoms, or a mixture of such lipids with synthetic or natural aliphatic compounds, The synthetic or natural aliphatic compound is preferably a compound of a vegetable source (for example, coconut oil) or an animal source (for example, tallow) and is preferably a vegetable-derived compound.

According to a feature of the present invention is a dry type, in particular in that the inorganic pigment moderate to strong H3O + ion-providers are selected from a strong acid medium to produce H ₃ O ⁺ ions to the mixture of strong acids or such acids, preferably selected from with an acid at 25 ℃ at less than or equal to the pK _a of 2.5.

In a very particular variable in accordance with a dry type wherein the inorganic pigment of the present invention in that the strong acid system having less than or equal to 0 the acid pK _a time selected from 25 ℃, such as sulfuric acid, hydrochloric acid or such mixture.

In another very special variant, the dry inorganic pigment according to the invention is characterized in that the medium strong acid or a plurality of medium strong acids are selected from pK having a k between 0 and 2.5 (including 2.5) at 25 °C. _a is an acid, more in particular selected from ^{_{H 2 SO 3, HSO 4 -}} , H ₃ PO ₄ or a mixture of such acids, and also may be formed more preferably selected from the divalent cation salts of strong acid medium, e.g. Calcium, which is hardly soluble in water, that is, has a solubility of less than 1% by mass.

In particular, the inorganic pigment according to the present invention is characterized in that the calcium carbonate is a natural calcium carbonate, and it is excellent that the natural calcium carbonate is selected from the group consisting of marble, calcite, chalk, limestone or a mixture thereof.

In a preferred mode, the dry inorganic pigment according to the invention is characterized by having a basis between 1 m ² /g and 200 m ² /g, preferably 5 m ² / measured according to the BET method. between g and 80 m ² / g and excellent between 20 m ² / g and a specific surface area between 60 m ² / g and measured by the Sedigraph ^TM 5100 using the measured between 0.1 and 50 microns, A median diameter between 1 and 10 microns is preferred.

The dry inorganic pigment according to the present invention is also characterized in that the humidity ratio is less than 1.50%, which is measured after drying at 120 ° C for 2 hours in an oven at atmospheric pressure.

According to the present invention, a dry inorganic pigment comprising a product formed in situ from a multiple reaction between calcium carbonate and the following: a reaction product of the carbonate and one or more medium to strong H3O+ ion donors is produced. Or a plurality of reaction products, and a method of the carbonate and a reaction product or a plurality of reaction products formed in situ and/or derived from externally supplied gaseous CO ₂ , and one or more compounds of the formula R-X) The feature is that the method comprises the following stages: a) treating the calcium carbonate in the aqueous phase with a medium strength to strong H3O+ ion donor and treating it with gaseous CO ₂ formed in situ, this treatment being necessary for stage a) Part, b) treating the calcium carbonate in the aqueous phase with a compound of formula R-X or a plurality of compounds, the point being that one or more compounds of formula R-X are before and/or during stage a) and/or Or added later, treated with one or more compounds of formula R-X, and more particularly with an R-X compound or compounds selected from the group consisting of fatty acids, aliphatic amines or aliphatic alcohols, Is it saturated? Which preferably has from 8 to 24 carbon atoms, such as stearic acid, oleic acid, linoleic acid, myristic acid, octanoic acid or a mixture of such lipids, preferably from 16 to 18 a carbon atom, or a mixture of such lipids with a synthetic or natural aliphatic compound, preferably a compound of vegetable origin (for example, coconut oil) or animal source (for example, butter) and a compound of vegetable origin, c) an anionic or cationic or weak anionic aqueous suspension of the product obtained in stage b) with a dry matter concentration between 1% and 80%, possibly using at least one An anionic or cationic or weak anionic electrolyte, which may be followed by repeated concentration, d) may add a base, preferably Ca(OH) ₂ , in order to increase the pH to above 6, preferably to 7.5 or more and more particularly increased to a value between 8 and 10, e) drying after one of the stages b), c) or d).

It should be noted that this drying stage e) is carried out by all drying methods well known to those skilled in the art.

In particular, the method according to the invention is characterized in that the calcium carbonate is a natural calcium carbonate, and it is excellent that the natural calcium carbonate is selected from the group consisting of marble, calcite, chalk, limestone or a mixture thereof.

More in particular, the method according to the present invention lines in that the moderate to strong H3O + ion providers selected based at processing conditions produce any medium strong acid H ₃ O ⁺ ions to the kind of strong acid or acids any mixture coefficient with respect to CaCO ₃ molar amounts to between 0.001 and 1 and preferably between 0.1 and 0.5 in accordance with the present invention, moderate to strong H3O + ion providers of mole fraction.

According to the present invention, the molar component of the R-X compound is generally between 0.0001 and 0.1 and preferably between 0.002 and 0.01 with respect to the molar number of CaCO ₃ .

According to a preferred embodiment, stage a) can be repeated several times, and the order of addition of the medium strong acid and strong acid is not added before and/or during and/or after the R-X compound is present as a medium strong acid or strong acid. Great significance.

According to a preferred embodiment, stage b) can be repeated several times.

Similarly, according to a preferred embodiment, the temperature during stage a) of the process is between 5 ° C and 100 ° C and preferably between 65 ° C and 80 ° C.

At the same time, it is preferred that the duration of stage a) of the process lasts between 0.01 and 10 hours, and preferably between 0.2 and 6 hours.

The treatment method according to the present invention is applied to a dilute, ordinary or extremely concentrated aqueous phase of a dry matter concentration, but may also be used in a suspension mixture of the various concentrations, preferably, the dry matter content is Between 1% by weight and 80% by weight.

In particular, a variant of stage c) uses from 0.01% to 5.0% by dry weight of an anionic electrolyte selected from the group consisting of the following monomers and which are unneutralized and partially neutralized Or a homopolymer or copolymer in an acid state which is completely neutralized: a monomer having an ethylenic unsaturation and having a monocarboxylic acid function, such as acrylic acid or methacrylic acid, or a diacid half ester such as a horse. a C ₁ to C ₄ monoester of acid or itaconic acid or a mixture thereof, or a monomer having a dicarboxylic acid function selected from the group consisting of having an ethylenic unsaturation and having a dicarboxylic acid function a monomer such as an acid anhydride such as crotonic acid, isocrotonic acid, cinnamic acid, isaconic acid or maleic acid or a carboxylic acid, such as maleic anhydride, or a monomer having a sulfonic acid function, which is selected from the group consisting of a chain-unsaturated monomer having a sulfonic acid function, such as acrylamido-methyl-propane-sulfonic acid, sodium methallylsulfonate, ethylenesulfonic acid and styrenesulfonic acid, or phosphoric acid a functional monomer selected from monomers having ethylenic unsaturation and having a phosphoric acid function, Such as ethylene phosphate, ethylene glycol (methacrylate) phosphate, propylene glycol (methacrylate) phosphate, ethylene glycol (acrylate) phosphate, propylene glycol (acrylate) phosphate and these ethoxylates Or a phosphonic acid-functional monomer selected from a monomer having an ethylenic unsaturation and having a phosphonic acid function, such as a vinylphosphonic acid or a mixture thereof, or a polyphosphate.

Similarly, a variant of stage c) is used, in particular a cationic electrolyte between 0.01% by dry weight and 5.0% by dry weight, selected from cationic monomers having ethylenic unsaturation Or a quaternary ammonium homopolymer or copolymer, such as [2-(methacryloxy)ethyl]trimethylammonium chloride or [2-(methacryloxy)oxy] Ethyl]ammonium trimethylammonium sulfate, [2-(acryloxy)ethyl]trimethylammonium chloride or [2-(acryloxy)ethyl]trimethylammonium sulfate, [3-( Acrylamide propyl]propyl]trimethylammonium chloride or [3-(acrylamido)propyl]trimethylammonium sulfate, dimethyldiallylammonium chloride or dimethyldiallyl Ammonium sulphate or [3-(methacryl oxime) propyl]trimethylammonium chloride or [3-(methacrylamido)propyl]trimethylammonium sulfate.

Similarly, a variant of stage c) is used, in particular a weak anionic electrolyte of from 0.01% to 5.0% by dry weight, selected from weakly ionic water-soluble copolymers, Including: a) at least one anionic monomer having a carboxylic acid or dicarboxylic acid or phosphoric acid or phosphonic acid or sulfonic acid function or a mixture thereof, b) at least one nonionic monomer, wherein the nonionic single system consists of Forming at least one monomer of formula (I):

(wherein: m and p represent the number of alkylene oxide units less than or equal to 150, n represents the number of ethylene oxide units less than or equal to 150, and q represents an integer at least equal to 1 such that 5 (m+n+p)q 150 and preferably 15 (m+n+p)q 120R ₁ represents hydrogen or methyl or ethyl, R ₂ represents hydrogen or methyl or ethyl, and R represents a group containing an unsaturated polymerizable function, preferably belonging to the group of ethylene, or belonging to acrylate or methacrylic acid. Ester, maleate, isoconate, crotonate, vinyl phthalate, or an unsaturated urethane such as acryloyl methacrylate, methacrylamide Acid ester, α-α' dimethyl-isopropenyl-benzyl carbamate, allyl urethane, or allyl ether or vinyl ether, whether or not substituted, or It belongs to the ethylenically unsaturated decylamine or quinone imine, and R' represents hydrogen or a hydrocarbon group having 1 to 40 carbon atoms, preferably represents a hydrocarbon group having 1 to 12 carbon atoms and is excellently represented. a hydrocarbon group having 1 to 4 carbon atoms), or a mixture of a plurality of monomers of the formula (I), c) possibly at least one propylene decyl decylamine or methacryl oxime amide monomer or Such derivatives, such as N-[3-(dimethylamino)propyl]propenylguanamine or N-[3-(dimethylamino)propyl]methylpropane An decyl decylamine and mixtures thereof, or at least one water-insoluble monomer, such as an alkyl acrylate or methacrylate, an unsaturated ester such as N-[2-(dimethylamino) Ethyl]methacrylate or N-[2-(dimethylamino)ethyl]acrylate, vinyls such as vinyl acetate, vinyl pyrrolidone, styrene, alpha-methyl styrene and a derivative, or at least one cationic monomer or quaternary ammonium, such as [2-(methacryloxy)ethyl]trimethylammonium chloride or [2-(methacryloxy) Ethyl]ammonium trimethylammonium sulfate, [2-(acryloxy)ethyl]trimethylammonium chloride or [2-(acryloxy)ethyl]trimethylammonium sulfate, [3-( Acrylamide propyl]propyl]trimethylammonium chloride or [3-(acrylamido)propyl]trimethylammonium sulfate, dimethyldiallylammonium chloride or dimethyldiallyl Ammonium sulphate or [3-(methacryl oxime) propyl]trimethylammonium chloride or [3-(methacrylamido)propyl]trimethylammonium sulfate, or at least one Organic fluorinated monomer or organic deuterated monomer, or several such singles Mixture, d) at least may be referred to as a grafting monomer content in the remainder of the present application is a monomer having at least two ethylenically chain unsaturation.

The dry inorganic pigment containing a product formed in situ according to the invention is characterized in that it is obtained by the process according to the invention.

More particularly, the inorganic pigment containing a product formed in situ according to the invention is characterized in that it has a specific surface area of between 1 m ² /g and 200 m ² /g as measured according to the BET method, It is preferably between 5 m ² /g and 80 m ² /g and very preferably between 20 m ² /g and 60 m ² /g and between 0.1 and 0.1 as measured by Sedigraph ^{T M} 5100 The median diameter between 50 microns, preferably between 1 and 10 microns.

The BET specific surface area was measured using the ISO 9277 method.

In another variant, the aqueous suspension of inorganic pigment obtained according to stages c) to d) is characterized in that the inorganic pigment has a mass of between 1 m ² /g and 200 m ² /g as measured using the BET method. a specific surface area between 5 m ² /g and 80 m ² /g and preferably between 10 m ² /g and 60 m ² /g and a measurement by Sedigraph ^{T M} 5100 Having a median diameter between 0.1 and 50 microns, preferably between 1 and 10 microns, and in the suspension having a dry matter content between 1% and 80%, and in The suspension contains at least one anionic electrolyte between 0.05% and 5.0% by dry weight relative to the dry weight of calcium carbonate.

The anionic electrolyte is selected from the anionic electrolytes mentioned above.

At the same time, more particularly, the aqueous inorganic pigment suspension obtained according to stages c) to d) is characterized in that the inorganic pigment has a mass of between 1 m ² /g and 200 m ² /g as measured using the BET method. The specific surface area between 5 m ² /g and 80 m ² /g and preferably between 20 m ² /g and 60 m ² /g and determined by measurement using Sedigraph ^{T M} 5100 a median diameter between 0.1 and 50 microns, preferably between 1 and 10 microns, and in the suspension having a dry matter content between 1% and 80%, and in the inorganic The aqueous pigment suspension contains at least one cationic electrolyte between 0.1% and 5.0% by dry weight relative to the dry weight of calcium carbonate.

The cationic electrolyte is selected from the cationic electrolytes mentioned above.

In a further special variant, the aqueous inorganic pigment suspension obtained according to stages c) to d) is characterized in that the inorganic pigment has a mass of between 1 m ² /g and 200 m ² as measured using the BET method. Between /g, preferably between 5 m ² /g and 80 m ² /g and very preferably between 20 m ² /g and 60 m ² /g, the specific surface area measured using the BET method and The median diameter between 0.1 and 50 microns, preferably between 1 and 10 microns, as determined by measurement using Sedigraph ^{T M} 5100, and in the suspension having between 0.3% and 80% The intervening dry matter content, and in the aqueous suspension of the inorganic pigment, is at least one weak anionic electrolyte between 15% and 60% by dry weight relative to the dry weight of the calcium carbonate.

Still more preferably, the aqueous suspension according to the invention is characterized in that the inorganic pigment has a relationship between 1 m ² /g and 80 m ² /g and preferably between 10 m ² /g and 60 The specific surface area between m ² /g and the median diameter between 0.1 and 50 microns, preferably between 1 and 10 microns, as determined by measurement using Sedigraph ^{T M} 5100.

The invention also relates to the use of the inorganic pigment suspension according to the invention as a rheology-regulating filler which allows the viscosity to be controlled while retaining the firmness of the plastisol formulation, the rigid PVC formulation, and more particularly Automotive industry, for the use of underbody protective covering formulations.

The invention also relates to the use of the inorganic pigment suspension according to the invention in the field of paints and/or coatings and/or high-paste coatings. The underbody protective covering according to the invention is characterized in that it has a serving fraction of 0.05 after drying. An inorganic filler according to the invention between between % and 50%, preferably between 1% and 20% and more preferably between 5% and 15%.

The following examples are illustrative of the invention, however, the scope is not limited.

EXAMPLE 1 This example illustrates the prior art and is directed to a variety of methods for preparing pigments according to the prior art.

Test No. 1 This test exemplifies a method for preparing a pigment according to the prior art. In order to prepare a pigment, 0.5 kg (in terms of dry pigment) is used as an aqueous suspension in a 10 liter vessel using distilled water. Having a dry content of 75% and dispersing with 0.6% sodium polyacrylate), a Norwegian marble type of natural calcium carbonate (which uses a Sedigraph ^{T M} 5100 from Micromeritics, Inc.) has a particle size analysis of 65 wt% of the particle system having less than 1 μm The diameter is diluted until an aqueous suspension having a dry matter concentration of 15% by weight is obtained. The suspension thus formed was later treated with 10% phosphoric acid (10% by weight solution) at 65 ° C while stirring at 500 rpm for 20 minutes. The pH was then adjusted to between 8 and 8.5 with a concentration of lime dry water equal to 10 dry weight percent prior to drying the resulting suspension using a Nara MSD 100 dryer.

The obtained inorganic pigment suspension had a dry pigment concentration equal to 18.8% by mass and a pH value equal to 8.4 before drying.

The particle size analysis measured using Sedigraph ^{T M} 5100 was that 90% by weight of the particle system had a diameter of less than 2 μm and 57% by weight of the particle system had a diameter of less than 1 μm.

After drying, the product had a BET specific surface area equal to 30.7 m ² /g as measured by the BET method using the ISO 9277 standard.

Test No. 2 This test exemplifies a method for preparing a pigment according to the prior art. In order to prepare a pigment, 0.758 kg (in terms of dry pigment) is used as an aqueous suspension in distilled water in a 10 liter ESCO reactor. (It has a dry content of 75% and is dispersed with 0.6% sodium polyacrylate), a natural chalk of the French chalk type (particle size analysis using a Sedigraph ^{T M} 5100 from Micromeritics, Inc.), 65% by weight of the particle system has a smaller The diameter of 1 μm was diluted until an aqueous suspension having a dry matter concentration of 10% by weight was obtained. The suspension thus formed was later treated with 20% phosphoric acid (20% by weight solution) at 65 ° C while stirring for 60 minutes. The pH was then adjusted to between 8 and 8.5 with a concentration of lime dry water equal to 10 dry weight percent prior to drying the resulting suspension using a Nara MSD 100 dryer.

The obtained inorganic pigment suspension had a dry pigment concentration equal to 18.8% by mass and a pH value equal to 8.4 before drying.

The particle size analysis measured using Sedigraph ^{T M} 5100 was 94.4% by weight of the particles having a diameter of less than 2 μm and 68.2% by weight of the particles having a diameter of less than 1 μm.

After drying, the product had a BET specific surface area equal to 31.1 m ² /g as measured by the BET method on the basis of ISO 9277.

Test No. 3 This test exemplifies a method for preparing a pigment according to the prior art. In order to prepare a pigment, 0.5 kg (in terms of dry pigment) is used as an aqueous suspension in a 10 liter vessel using distilled water. Having a dry content of 75% and dispersing with 0.6% sodium polyacrylate), a Norwegian marble type of natural calcium carbonate (particle size analysis using a Sedigraph ^{T M} 5100 from Micromeritics), 65% by weight of the granules having less than 1 μm The diameter was diluted until an aqueous suspension having a dry matter concentration of 15% by weight was obtained. The suspension thus formed was later treated with 10% phosphoric acid (10% by weight solution) at 65 ° C while stirring at 500 rpm for 20 minutes. The pH was then adjusted to between 8 and 8.5 with a concentration of lime dry water equal to 10 dry weight percent prior to drying the resulting suspension using a Nara MSD 100 dryer.

The obtained inorganic pigment suspension had a dry pigment concentration equal to 18.8% by mass and a pH value equal to 8.4 before drying.

The particle size analysis measured using Sedigraph ^{T M} 5100 was that 90% by weight of the particle system had a diameter of less than 2 μm and 57% by weight of the particle system had a diameter of less than 1 μm.

After drying, the product had a BET specific surface area equal to 30.7 m ² /g as measured by the BET method using the ISO 9277 standard.

The product was then treated with 3% stearic acid. The treatment was carried out in a laboratory grade mixer manufactured by MTI at 120 ° C for ten minutes; the rotation speed was 1500 rpm.

EXAMPLE 2 This example illustrates the invention and relates to the manufacture of a dry inorganic pigment comprising a product formed in situ from a multiplex reaction between natural calcium carbonate and the following: the carbonate and one or more medium strengths a reaction product or products of a strong H ₃ O ⁺ ion donor, a reaction product or products of the carbonate and in situ formed and/or derived from externally supplied gaseous CO ₂ , and one or more A method of the compound of the formula R-X) and an inorganic pigment obtained by the method.

Test No. 4 This test is illustrative of the invention and relates to a process for obtaining a pigment according to the invention in which 2% of a mixture of palmitic acid and stearic acid (at a ratio of about 1/1 by weight) The treatment occurs during the reaction of calcium carbonate and phosphoric acid.

To complete this test, 0.746 kg (based on dry pigment) was used as an aqueous suspension (with a dry content of 78%, dispersed with 0.5% sodium polyacrylate) using distilled water in a 10 liter ESCO reactor. The natural chalk of the French chalk type (particle size analysis measured by Sedigraph ^{T M} 5100 of Micromeritics Co., Ltd. is 65% by weight of the particle system having a diameter of less than 1 μm) is diluted until an aqueous suspension having a dry matter concentration of 10% by weight is obtained. The suspension thus formed was later treated with 25% phosphoric acid (20% by weight solution) at 60 ° C while stirring at 500 rpm for 60 minutes. Then, before drying the resulting suspension using a Nara MSD 100 dryer, a palmitic acid/stearic acid mixture type (in a ratio of 1/1 by weight) of 2% fatty acid was added in powder form and mixed for 30 minutes.

The obtained inorganic pigment suspension had a dry pigment concentration equal to 9.5% by mass and a pH value equal to 6.4 before drying.

The particle size analysis measured using Sedigraph ^{T M} 5100 was 90.9 wt% of the particle system having a diameter of less than 2 μm and 66.8 wt% of the particle system having a diameter of less than 1 μm.

After drying, the product has a BET specific surface area equal to 33.4 m ² /g as measured by the BET method using ISO 9277, and a median equal to 0.72 μm as measured by a Sedigraph ^{T M} 5100 measurement. The diameter and the moisture content equal to 1.32% as determined using the above method.

Test No. 5 This test is illustrative of the present invention and relates to a process for obtaining a pigment according to the present invention, in which a treatment with 2% stearic acid occurs before the reaction of calcium carbonate and phosphoric acid.

To complete this test, 0.750 kg (based on dry pigment) was used as an aqueous suspension (with a dry content of 78% and dispersed with 0.5% sodium polyacrylate) in a 10 liter vessel using a distilled water, a French The natural calcium carbonate of the chalk type (using a particle size analysis measured by SemerTaph ^{T M} 5100 of Micromeritics Co., Ltd. is a particle size of 65% by weight having a diameter of less than 1 μm) is diluted until an aqueous suspension having a dry matter concentration of 10% by weight is obtained. Later, 2% pure stearic acid (from Fluka) was added and heated until the suspension thus formed was treated with 25% phosphoric acid (20% by weight solution) at 60 ° C while stirring at 500 rpm for 60 minutes. Mix at 70 ° C for 15 minutes. The suspension was allowed to react for 30 minutes before drying the suspension thus obtained using a Nara MSD-100 dryer.

The resulting inorganic pigment suspension had a dry pigment concentration equal to 9.4% by mass and a pH value equal to 6.4 before drying.

The particle size analysis measured using Sedigraph ^{T M} 5100 was 91.7 wt% of the particle system having a diameter of less than 2 μm and 66.9 wt% of the particle system having a diameter of less than 1 μm.

After drying, the product has a BET specific surface area equal to 34.5 m ² /g as measured by the BET method using ISO 9277 and a median equal to 0.73 μm as measured by a Sedigraph ^{T M} 5100 measurement. diameter.

Test No. 6 This test is illustrative of the present invention and relates to a process for obtaining a pigment according to the present invention, in which a treatment with 3% stearic acid occurs before the reaction of calcium carbonate and phosphoric acid.

To complete this test, 0.750 kg (based on dry pigment) was used as an aqueous suspension (with a dry content of 78% and dispersed with 0.5% sodium polyacrylate) in a 10 liter vessel using distilled water, a French white peony A type of natural calcium carbonate (particle size analysis as measured by Sedigraph ^{T M} 5100 from Micromeritics, Inc. is 65% by weight of the particles having a diameter of less than 1 μm) is diluted until an aqueous suspension having a dry matter concentration of 10% by weight is obtained. Later, 3% 3% pure stearic acid (from Fluka) was first treated by cooling it to 60 ° C and treating the thus formed suspension with 25% phosphoric acid (20% by weight solution) while stirring at 500 rpm for 60 minutes. ), heated to 70 ° C and mixed for 15 minutes. The suspension was allowed to react for 30 minutes before drying the suspension thus obtained using a Nara MSD 100 dryer.

The resulting inorganic pigment suspension had a dry pigment concentration equal to 9.5% by mass and a pH value equal to 6.4 before drying.

The particle size analysis measured using Sedigraph ^{T M} 5100 was that 93.0% by weight of the particle system had a diameter of less than 2 μm and that 73.1% by weight of the particle system had a diameter of less than 1 μm.

After drying, the product has a BET specific surface area equal to 28.8 m ² /g as measured by the BET method using ISO 9277 and a median equal to 0.57 μm as measured by a Sedigraph ^{T M} 5100 measurement. diameter.

Test No. 7 This test is illustrative of the present invention and relates to a process for obtaining a pigment according to the present invention, in which a treatment with 5% stearic acid occurs before the reaction of calcium carbonate and phosphoric acid.

To complete this test, 0.750 kg (based on dry pigment) was used as an aqueous suspension (with a dry content of 78% and dispersed with 0.5% sodium polyacrylate) in a 10 liter vessel using distilled water, a French white peony A type of natural calcium carbonate (particle size analysis as measured by Sedigraph ^{T M} 5100 from Micromeritics, Inc. is 65% by weight of the particles having a diameter of less than 1 μm) is diluted until an aqueous suspension having a dry matter concentration of 10% by weight is obtained. Later, 5% pure stearic acid (from Fluka) was first treated by cooling it to 60 ° C and treating the thus formed suspension with 25% phosphoric acid (20% by weight solution) while stirring at 500 rpm for 60 minutes. ), heated to 70 ° C and mixed for 15 minutes. The suspension was allowed to react for 30 minutes before drying the suspension thus obtained using a Nara MSD 100 dryer.

The obtained inorganic pigment suspension had a dry pigment concentration equal to 9.6 mass% and a pH value equal to 6.4 before drying.

The particle size analysis measured using Sedigraph ^{T M} 5100 was 85.3 wt% of the particle system having a diameter of less than 2 μm and 61.9% by weight of the particle system having a diameter of less than 1 μm.

After drying, the product has a BET specific surface area equal to 26.5 m ² /g as measured by the BET method using ISO 9277 and a median equal to 0.75 μm as measured by a Sedigraph ^{T M} 5100 measurement. diameter.

Test No. 8 This test is illustrative of the present invention and relates to a process for obtaining a pigment according to the present invention, in which a treatment with 2% stearic acid occurs during the reaction of calcium carbonate and phosphoric acid.

To complete this test, 200 kg (in dry pigment) was used as an aqueous suspension (with a dry content of 78% and dispersed with 0.5% sodium polyacrylate) in a 3000 liter vessel using distilled water. The French chalk type natural calcium carbonate (particle size analysis measured by Sedigraph ^{T M} 5100 of Micromeritics Co., Ltd. is 65% by weight of the particle system having a diameter of less than 1 μm) is diluted until an aqueous suspension having a dry matter concentration of 10% by weight is obtained. . The suspension thus formed was later treated with 36% phosphoric acid (10% by weight solution) at 70 ° C while stirring at 500 rpm for 120 minutes. Then, 2% stearic acid (having a technical quality equivalent to a C16-C18 mixture) in powder form was added and mixed for 30 minutes before drying the suspension thus obtained using a Nara MSD 100 dryer.

The resulting inorganic pigment suspension had a dry pigment concentration equal to 9.2% by mass and a pH value equal to 6.8 before drying.

The particle size analysis measured using Sedigraph ^{T M} 5100 was that 74.2% by weight of the particle system had a diameter of less than 2 μm and 37.5% by weight of the particle system had a diameter of less than 1 μm.

After drying, the product has a BET specific surface area equal to 31.4 m ² /g as measured by the BET method using ISO 9277, and a median equal to 1.31 μm as measured by a Sedigraph ^{T M} 5100 measurement. The diameter and the moisture content equal to 1.40% as determined using the above method.

Test No. 9 This test is illustrative of the present invention and relates to a process for obtaining a pigment according to the present invention, in which a treatment with 2% stearic acid occurs during the reaction of calcium carbonate and phosphoric acid, but Before the acid is added.

In order to complete this test, a 135 liter L Dige-type fluidized bed using distilled water, 9 kg (as dry pigment) in the form of an aqueous suspension (which has a dry content of 78% and dispersed with 0.5% sodium polyacrylate), a natural type of French white peony Calcium (particle size analysis as measured by Sedigraph ^{T M} 5100 from Micromeritics, Inc., 65% by weight of the particles having a diameter of less than 1 μm) was diluted until an aqueous suspension having a dry matter concentration of 10% by weight was obtained. The suspension thus formed was later treated with 13% phosphoric acid (10% by weight solution) at 70 ° C while stirring at 500 rpm for 24 minutes. Then, 2% stearic acid (having a technical quality equivalent to a C16-C18 mixture) in powder form was added and mixed for 30 minutes before drying the suspension thus obtained using a Nara MSD-100 dryer.

The resulting inorganic pigment suspension had a dry pigment concentration equal to 8.2% by mass and a pH value equal to 7.1 before drying.

The particle size analysis measured using Sedigraph ^{T M} 5100 was 87.6 wt% of the particles having a diameter of less than 2 μm and 59.3% by weight of the particles having a diameter of less than 1 μm.

After drying, the product has a BET specific surface area equal to 21.7 m ² /g as measured by the BET method using ISO 9277 and a median equal to 0.83 μm as measured by a Sedigraph ^{T M} 5100 measurement. diameter.

Test No. 10 This test is illustrative of the present invention and relates to a process for obtaining a pigment according to the present invention, in which a treatment with 1% stearic acid occurs before the reaction of calcium carbonate and phosphoric acid.

To complete this test, 0.750 kg (in dry pigment) was used as an aqueous suspension (dry content of 75%, dispersed with 0.45% polyacrylic acid) in a 10 liter ESCO reactor using a distilled water. The French chalk type natural calcium carbonate (particle size analysis measured by Sedigraph ^{T M} 5100 of Micromeritics Co., Ltd. is 65% by weight of the particle system having a diameter of less than 1 μm) is diluted until an aqueous suspension having a dry matter concentration of 10% by weight is obtained. . A 1% stearic acid in powder form (a C16-C18 mixture of technical grade equivalent to the palmitic acid/stearic acid form) was then added and the mixture was mixed for 15 minutes. The suspension thus formed was later treated with 10% phosphoric acid (20% by weight solution) at 60 ° C while stirring for 60 minutes. The suspension was allowed to react for 30 minutes before drying the suspension thus obtained using a Nara MSD-100 dryer.

The obtained inorganic pigment suspension had a dry pigment concentration equal to 9.6 mass% and a pH value equal to 6.6 before drying.

The particle size analysis measured using Sedigraph ^{T M} 5100 was that 94.8 wt% of the particles had a diameter of less than 2 μm and 67.0 wt% of the particles had a diameter of less than 1 μm.

After drying, the product has a BET specific surface area equal to 18.9 m ² /g as measured by the BET method using ISO 9277 and a median equal to 0.73 μm as measured by a Sedigraph ^{T M} 5100 measurement. diameter.

Test No. 11 This test is illustrative of the present invention and relates to a process for obtaining a pigment according to the present invention, in which a treatment with 0.5% stearic acid occurs before the reaction of calcium carbonate and phosphoric acid.

To complete this test, 0.750 kg (as dry pigment) was used as an aqueous suspension (with a dry content of 75% and dispersed with 0.5% sodium polyacrylate) in a 10 liter ESCO reactor using distilled water, A natural chalk of the French chalk type (using a particle size analysis measured by a Sedigraph ^{T M} 5100 from Micromeritics, Inc., 65% by weight of the particles having a diameter of less than 1 μm) is diluted until an aqueous suspension having a dry matter concentration of 10% by weight is obtained. liquid. 0.5% stearic acid (technical quality equivalent to a C16-C18 mixture) was then added and the mixture was mixed for 15 minutes. The suspension thus formed was treated with 20% phosphoric acid (20% by weight solution) at 60 ° C and stirred simultaneously for 60 minutes. The suspension was allowed to react for 30 minutes before drying the suspension thus obtained using a Nara MSD-100 dryer.

The obtained inorganic pigment suspension had a dry pigment concentration equal to 9.3 mass% and a pH value equal to 6.6 before drying.

The particle size analysis measured using Sedigraph ^{T M} 5100 was that 94.8 wt% of the particles had a diameter of less than 2 μm and 68.2% by weight of the particles had a diameter of less than 1 μm.

After drying, the product has a BET specific surface area equal to 32.1 m ² /g as measured by the BET method using ISO 9277 and a median equal to 0.74 μm as measured by a Sedigraph ^{T M} 5100 measurement. diameter.

Test No. 12 This test is illustrative of the present invention and relates to a process for obtaining a pigment according to the present invention, in which a treatment with 1% stearic acid occurs before the reaction of marble-like calcium carbonate and phosphoric acid.

To complete this test, 0.750 kg (based on dry pigment) was used as an aqueous suspension (with a dry content of 78% and dispersed with 0.62% sodium polyacrylate) in distilled water using a 10 liter ESCO reactor. A natural marble of the Norwegian marble type (particle size analysis measured by Sedigraph ^{T M} 5100 from Micromeritics, Inc., 65% by weight of the granules having a diameter of less than 1 μm) is diluted until an aqueous suspension having a dry matter concentration of 10% by weight is obtained . Then 1% stearic acid (technical quality equivalent to a C16-C18 mixture) was added and the mixture was mixed for 15 minutes. The suspension thus formed was treated with 20% phosphoric acid (20% by weight solution) at 60 ° C and stirred simultaneously for 60 minutes. The suspension was allowed to react for 30 minutes before drying the suspension thus obtained using a Nara MSD-100 dryer.

The obtained inorganic pigment suspension had a dry pigment concentration equal to 9.5% by mass and a pH value equal to 6.6 before drying.

The particle size analysis measured using Sedigraph ^{T M} 5100 was 89.6 wt% of the particles having a diameter of less than 2 μm and 64.5 wt% of the particles having a diameter of less than 1 μm.

After drying, the product has a BET specific surface area equal to 40.2 m ² /g as measured by the BET method using ISO 9277, and a median equal to 0.75 μm as measured by a Sedigraph ^{T M} 5100 measurement. The diameter and the moisture content equal to 1.41% as determined using the above method.

Test No. 13 This test is illustrative of the present invention and relates to a process for obtaining a pigment according to the present invention, in which the test system uses Winnofil SPT from Solvay Corporation, which is a precipitated calcium carbonate treated with a fatty acid. The particle size analysis of Winnofil SPT measured using Sedigraph ^{T M} 5100 is that 89.6 % of the particles have a diameter of less than 2 μm and 64.5% of the particles have a diameter of less than 1 μm and the BET specific surface area is equal to 17.8 m ² /g ( The treatment with stearic acid occurred before the reaction of calcium carbonate and phosphoric acid by the BET method of ISO 9277.

To complete this test, 0.750 kg (as dry pigment) was used as an aqueous suspension (with a dry content of 78% and dispersed with 0.5% sodium polyacrylate) in a 10 liter ESCO reactor using distilled water. The Winnofil SPT was diluted until an aqueous suspension having a dry matter concentration of 10% by weight was obtained. Then, the thus-prepared suspension was treated with 20% phosphoric acid (20% by weight solution) at 60 ° C while stirring the suspension thus obtained, using a Nara MSD-100 dryer, for 60 minutes.

The resulting inorganic pigment suspension had a dry pigment concentration equal to 9.3% by mass and a pH value equal to 6.4 before drying.

The particle size analysis measured using Sedigraph ^{T M} 5100 was 62.9 wt% of the particle system having a diameter of less than 2 μm and 51.4 wt% of the particle system having a diameter of less than 1 μm.

After drying, the product has a BET specific surface area equal to 52.1 m ² /g as measured by the BET method using ISO 9277 and a median equal to 0.90 μm as measured by a Sedigraph ^{T M} 5100 measurement. diameter.

Test No. 14 This test is illustrative of the present invention and relates to a process for obtaining a pigment according to the present invention, in which the test system uses Socal 322 from Solvay Co., which is a precipitated calcium carbonate treated with a fatty acid. The particle size analysis measured using Sedigraph ^{T M} 5100 is 90.0% of the particle system has a diameter of less than 2 μm and 86.0% of the particle system has a diameter of less than 1 μm, and the BET specific surface area is equal to 17.5 m ² /g (to adopt ISO The 9277 benchmark BET method measured)), so the treatment with stearic acid occurred before the reaction of calcium carbonate and phosphoric acid.

To complete this test, 0.750 kg (as dry pigment) was used as an aqueous suspension (with a dry content of 78% and dispersed with 0.5% sodium polyacrylate) in a 10 liter ESCO reactor using distilled water. Socal 322 was diluted until an aqueous suspension having a dry matter concentration of 10% by weight was obtained. Then, the thus-prepared suspension was treated with 20% phosphoric acid (20% by weight solution) at 60 ° C while stirring the suspension thus obtained, using a Nara MSD-100 dryer, for 60 minutes.

The obtained inorganic pigment suspension had a dry pigment concentration equal to 9.3% by mass and a pH value equal to 6.3 before drying.

The particle size analysis measured using Sedigraph ^{T M} 5100 was 87.9 wt% of the particle system having a diameter of less than 2 μm and 77.9 wt% of the particle system having a diameter of less than 1 μm.

After drying, the product has a BET specific surface area equal to 48.4 m ² /g as measured by the BET method using ISO 9277 and a median equal to 0.30 μm as measured by a Sedigraph ^{T M} 5100 measurement. diameter.

Test No. 15 This test is illustrative of the present invention and relates to a process for obtaining a pigment according to the present invention, in which a treatment of a mixture of 2% fatty acid and a fatty alcohol occurs in a reaction of chalky calcium carbonate and phosphoric acid. prior to.

To complete this test, 0.750 kg (as dry pigment) was used as an aqueous suspension (with a dry content of 75% and dispersed with 0.5% sodium polyacrylate) in a 10 liter ESCO reactor using distilled water, A natural chalk of the French chalk type (using a particle size analysis measured by a Sedigraph ^{T M} 5100 from Micromeritics, Inc., 65% by weight of the particles having a diameter of less than 1 μm) is diluted until an aqueous suspension having a dry matter concentration of 10% by weight is obtained. liquid. Then 0.2% vegetable oil-based fatty acid (Hobum Oleochemicals (Hamburg, Germany) sold under the trade name "isomergine" acid) and 1.8% stearyl acid were added and the mixture was mixed for 15 minutes; The suspension thus formed was treated with 25% phosphoric acid (30% by weight solution) at 60 ° C while stirring for 60 minutes. The suspension was allowed to react for 30 minutes before drying the suspension thus obtained using a Nara MSD-100 dryer.

The obtained inorganic pigment suspension had a dry pigment concentration equal to 9.8% by mass and a pH value equal to 6.0 before drying.

The particle size analysis measured using Sedigraph ^{T M} 5100 was that 74.1% by weight of the particle system had a diameter of less than 2 μm and 38.0% by weight of the particle system had a diameter of less than 1 μm.

After drying, the product has a BET specific surface area equal to 24.0 m ² /g as measured by the BET method using ISO 9277 and a median equal to 1.29 μm as measured by a Sedigraph ^{T M} 5100 measurement. diameter.

Test No. 16 This test is illustrative of the present invention and relates to a process for obtaining a pigment according to the present invention, in which a treatment of a mixture of 2% fatty acid and a fatty alcohol occurs in a reaction of chalky calcium carbonate and phosphoric acid. prior to.

To complete this test, 0.750 kg (in dry pigment) was used as an aqueous suspension (with a dry content of 65%, dispersed with 0.13% polyacrylic acid) in a 10 liter ESCO reactor, a French The natural calcium carbonate of the chalk type (using a particle size analysis measured by a Sedigraph ^{T M} 5100 from Micromeritics, Inc., 32% by weight of the particles having a diameter of less than 1 μm) was diluted until an aqueous suspension having a dry matter concentration of 10% by weight was obtained. Then 0.5% vegetable oil-based fatty acid (Hobum Oleochemicals (Hamburg, Germany) sold under the trade name "isomergine" acid) and 1.5% dodecenol were added and the mixture was mixed for 15 minutes; The suspension thus formed was treated with 25% phosphoric acid (30% by weight solution) at 60 ° C while stirring for 60 minutes. The suspension was allowed to react for 30 minutes before drying the suspension thus obtained using a Nara MSD-100 dryer.

The obtained inorganic pigment suspension had a dry pigment concentration equal to 9.8% by mass and a pH value equal to 6.0 before drying.

The particle size analysis measured using Sedigraph ^{T M} 5100 was that 57.3 wt% of the particles had a diameter of less than 2 μm and 25.3% by weight of the particles had a diameter of less than 1 μm.

After drying, the product has a BET specific surface area equal to 31.0 m ² /g as measured by the BET method using ISO 9277 and a median equal to 1.79 μm as measured by a Sedigraph ^{T M} 5100 measurement. diameter.

Test No. 17 This test is illustrative of the present invention and relates to a process for obtaining a pigment according to the present invention, in which a treatment with 2% fatty acid occurs before the reaction of chalky calcium carbonate and phosphoric acid.

To complete this test, 0.750 kg (as dry pigment) was used as an aqueous suspension (with a dry content of 65% and dispersed with 0.13 % sodium polyacrylate) in a 10 liter ESCO reactor using distilled water, A natural chalk of the French chalk type (using a particle size analysis measured by a Sedigraph ^{T M} 5100 from Micromeritics, Inc., 32% by weight of the particles having a diameter of less than 1 μm) is diluted until an aqueous suspension having a dry matter concentration of 10% by weight is obtained. liquid. Then 2.0% stearyl alcohol was added and the mixture was mixed for 15 minutes; then the suspension thus formed was treated with 25% phosphoric acid (30% by weight solution) at 60 ° C while stirring for 60 minutes. The suspension was allowed to react for 30 minutes before drying the suspension thus obtained using a Nara MSD-100 dryer.

The obtained inorganic pigment suspension had a dry pigment concentration equal to 9.8% by mass and a pH value equal to 6.1 before drying.

The particle size analysis measured using Sedigraph ^{T M} 5100 was that 74.8 wt% of the particle system had a diameter of less than 2 μm and that 36.8 wt% of the particle system had a diameter of less than 1 μm.

After drying, the product has a BET specific surface area equal to 23.9 m ² /g as measured by the BET method using ISO 9277 and a median equal to 1.30 μm as measured by a Sedigraph ^{T M} 5100 measurement. diameter.

Test No. 18 This test is illustrative of the invention and relates to a process for obtaining a pigment according to the invention in which the treatment with 2% stearic acid is carried out in the manufacture of precipitated calcium carbonate and at medium strength to strong The period of the H ₃ O ⁺ ion donor treatment is continuously performed.

To complete this test, the process was carried out as follows: 400 grams of Ca(OH) ₂ was prepared in 7600 grams of distilled water in a 10 liter ESCO reactor, followed by the addition of gaseous CO ₂ at 30 ° C until A pH equal to 6.5.

After allowing to react for 30 minutes, the suspension was heated to 60 ° C in the reactor, after which 2.0% stearic acid was added and the mixture was mixed for 15 minutes; then 20% phosphoric acid (30% by weight) Solution The suspension thus formed was treated while stirring for 60 minutes. The suspension was allowed to react for 30 minutes before drying the suspension thus obtained using a Nara MSD-100 dryer.

The obtained inorganic pigment suspension had a dry pigment concentration equal to 5.7% by mass and a pH value equal to 6.4 before drying.

The particle size analysis measured using Sedigraph ^{T M} 5100 was that 41.4% by weight of the particles had a diameter of less than 2 μm and 18.1% by weight of the particles had a diameter of less than 1 μm.

After drying, the product has a BET specific surface area equal to 37.9 m ² /g as measured by the BET method using ISO 9277 and a median equal to 2.29 μm as measured by a Sedigraph ^{T M} 5100 measurement. diameter.

Test No. 19 This test is illustrative of the present invention and relates to a process for obtaining a pigment according to the present invention, in which a treatment with 1% fatty acid occurs before the reaction of chalky calcium carbonate and phosphoric acid.

To complete this test, 0.750 kg (based on dry pigment) was used as an aqueous suspension (with a dry content of 75% and dispersed with 0.6% sodium polyacrylate) in a 10 liter ESCO reactor using distilled water. A natural chalk of the French chalk type (particle size analysis measured by Sedigraph ^{T M} 5100 from Micromeritics, Inc., 50% by weight of the particles having a diameter of less than 1 μm) is diluted until an aqueous suspension having a dry matter concentration of 10% by weight is obtained . 1.0% stearic acid was added later and the mixture was mixed for 15 minutes. The suspension thus formed was then treated with 25% phosphoric acid (20% by weight solution) at 60 ° C while stirring for 60 minutes. The suspension was allowed to react for 30 minutes before drying the suspension thus obtained using a Nara MSD-100 dryer.

The resulting inorganic pigment suspension had a dry pigment concentration equal to 9.3% by mass and a pH value equal to 6.5 before drying.

The particle size analysis measured using Sedigraph ^{T M} 5100 was 94.9 wt% of the particle system having a diameter of less than 2 μm and 67.0 wt% of the particle system having a diameter of less than 1 μm.

After drying, the product has a BET specific surface area equal to 34.9 m ² /g as measured by the BET method using ISO 9277 and a median equal to 0.76 μm as measured by a Sedigraph ^{T M} 5100 measurement. diameter.

Test No. 20 This test is illustrative of the present invention and relates to a process for obtaining a pigment according to the present invention, in which a treatment with 1% fatty acid occurs after the reaction of chalky calcium carbonate and phosphoric acid.

To complete this test, 0.750 kg (based on dry pigment) was used as an aqueous suspension (with a dry content of 75% and dispersed with 0.6% sodium polyacrylate) in a 10 liter ESCO reactor using distilled water. A natural chalk of the French chalk type (particle size analysis measured by Sedigraph ^{T M} 5100 from Micromeritics, Inc., 50% by weight of the particles having a diameter of less than 1 μm) is diluted until an aqueous suspension having a dry matter concentration of 10% by weight is obtained . The suspension thus formed was then treated with 20% phosphoric acid (20% by weight solution) at 60 ° C while stirring at 500 rpm for 60 minutes. Then, 1.0% stearic acid in the form of a powder was added and mixed for 30 minutes before drying the suspension thus obtained using a Nara MSD-100 dryer.

The obtained inorganic pigment suspension had a dry pigment concentration equal to 9.5% by mass and a pH value equal to 6.5 before drying.

The particle size analysis measured using Sedigraph ^{T M} 5100 was 94.1% by weight of the particles having a diameter of less than 2 μm and 66.2% by weight of the particles having a diameter of less than 1 μm.

After drying, the product has a BET specific surface area equal to 30.4 m ² /g as measured by the BET method using ISO 9277 and a median equal to 0.77 μm as measured by a Sedigraph ^{T M} 5100 measurement. diameter.

Test No. 21 This test is illustrative of the present invention and relates to a process for obtaining a pigment according to the present invention, in which a treatment with 2% dodecylbenzenesulfonic acid occurs in chalky calcium carbonate and phosphoric acid. After the reaction.

To complete this test, 0.750 kg (in dry pigment) was used as an aqueous suspension (with a dry content of 75%, dispersed with 0.6% sodium polyacrylate) in a 10 liter ESCO reactor using a distilled water, a French The natural calcium carbonate of the chalk type (using a particle size analysis measured by a Sedigraph ^{T M} 5100 from Micromeritics, Inc., 50% by weight of the particles having a diameter of less than 1 μm) was diluted until an aqueous suspension having a dry matter concentration of 10% by weight was obtained. The suspension thus formed was then treated with 25% phosphoric acid (30% by weight solution) at 60 ° C while stirring at 500 rpm for 60 minutes. Then, 2.0% dodecylbenzenesulfonic acid in the form of a powder was added and mixed for 30 minutes before the suspension thus obtained was dried using a Nara MSD-100 dryer.

The obtained inorganic pigment suspension had a dry pigment concentration equal to 10.0% by mass and a pH value equal to 6.6 before drying.

The particle size analysis measured using Sedigraph ^{T M} 5100 was 93.9 wt% of the particles having a diameter of less than 2 μm and the 59.6% by weight of the particles having a diameter of less than 1 μm.

After drying, the product has a BET specific surface area equal to 35.4 m ² /g as measured by the BET method using ISO 9277 and a median equal to 0.87 μm as measured by a Sedigraph ^{T M} 5100 measurement. diameter.

Test No. 22 This test is illustrative of the present invention and relates to a process for obtaining a pigment according to the present invention, in which a treatment with 2% lauric acid occurs after the reaction of marble-like calcium carbonate and phosphoric acid.

To complete this test, 0.750 kg (based on dry pigment) was used as an aqueous suspension (with a dry content of 78% and dispersed with 0.62% sodium polyacrylate) in distilled water using a 10 liter ESCO reactor. A natural marble of the Norwegian marble type (particle size analysis measured by Sedigraph ^{T M} 5100 from Micromeritics, Inc., 65% by weight of the granules having a diameter of less than 1 μm) is diluted until an aqueous suspension having a dry matter concentration of 10% by weight is obtained . The suspension thus formed was then treated with 20% phosphoric acid (30% by weight solution) at 60 ° C while stirring for 60 minutes. Then, 2.0% of lauric acid was added and mixed for 30 minutes before drying the suspension thus obtained using a Nara MSD-100 dryer.

The obtained inorganic pigment suspension had a dry pigment concentration equal to 9.8% by mass and a pH value equal to 6.8 before drying.

The particle size analysis measured using Sedigraph ^{T M} 5100 was 88.8 wt% of the particle system having a diameter of less than 2 μm and 64.8 wt% of the particle system having a diameter of less than 1 μm.

After drying, the product has a BET specific surface area equal to 35.0 m ² /g as measured by the BET method using ISO 9277, and a median equal to 0.65 μm as measured by a Sedigraph ^{T M} 5100 measurement. The diameter and the moisture content equal to 1.26 % as determined using the above method.

EXAMPLE 3 This example relates to the use of a pigment according to the invention as a rheology modifier for the preparation of a polyvinyl chloride (PVC) based plastisol.

The charged plastisol is produced by mixing a PVC-based uncharged plastisol with calcium carbonate (or a test inorganic pigment) in a container measuring 7 cm in diameter and using a spatula. . The total weight of the mixture was 200 grams. The mixture was then dispersed for two minutes using a "Pendraulik" ^{T M} LD50 laboratory grade mixer with a dispersion disk diameter of 5 cm and a dispersion disk speed of 2700 rpm (manually adjusted to position No. 3).

When the dispersion was completed, the viscosity was measured at 20 ° C using a "Rheomat 120" ^{T M} machine (measuring machine according to DIN 125).

After aging for 24 hours and 30 days at a temperature of 23 ° C, the pour point was measured using a Bingham model, which is well known to those skilled in the art.

In all the tests of the examples, the test target is to obtain a weight-reduced automobile body with a first-class change and made of a fixed formula. The formula of PVC (polyvinyl chloride)-based plastisol is below Formulation 1 was used as its formulation: -90% by weight of Henkel-Teroson's PVC resin plastisol, -10% by weight of inorganic filler for testing.

Test No. 23 This test is a prior art and uses precipitated calcium carbonate sold by the company Solvay under the trade name Winnofil SPT ^{T M.} This test is used as a reference.

Test No. 24 This test illustrates the prior art and uses calcium carbonate from Test No. 1. The pour point after aging for 30 days at a temperature of 23 ° C in Formulation 1 was 63.6%, which was higher than the pour point of the No. 23 test.

Test No. 25 This test exemplifies the prior art and uses calcium carbonate treated with 3% stearic acid and dried from the No. 3 test. The treatment was carried out in a laboratory grade mixer manufactured by MTI at 120 ° C for ten minutes; the rotation speed was 1500 rpm. The pour point after aging for 30 days at a temperature of 23 ° C in Formulation 1 was 49.0 %, which was lower than the pour point of the No. 23 test.

The treatment after drying does not work.

Test No. 26 This test is a prior art and uses precipitated calcium carbonate sold by Solvay under the trade name Socal ^{T M} 322. The pour point after aging for 30 days at a temperature of 23 ° C in Formulation 1 was 16.8%, which was higher than the pour point of the No. 23 test.

Test No. 27 This test exemplifies the prior art and uses calcium carbonate sold under the trade name of Hydrocarb ^{T M} 120T by Omya Corporation. The pour point after aging for 30 days at a temperature of 23 ° C in Formulation 1 was 7.7%, which was lower than the pour point of the No. 23 test.

Test No. 28 This test exemplifies the prior art and uses calcium carbonate sold under the trade name Omyabond ^{T M} 302 by Omya Corporation. The pour point after aging for 30 days at a temperature of 23 ° C in Formulation 1 was 1.4%, which was higher than the pour point of the No. 23 test.

Test No. 29 This test exemplifies the prior art and uses calcium carbonate sold under the trade name Omyabond ^{T M} 301 by Omya Corporation. The pour point after aging for 30 days at a temperature of 23 ° C in Formulation 1 was 24.5%, which was lower than the pour point of the No. 23 test.

Test No. 30 This test exemplifies the present invention and uses calcium carbonate tested in No. 4. The pour point after aging for 30 days at a temperature of 23 ° C in Formulation 1 was 53.1%, which was higher than the pour point of the No. 23 test.

Test No. 31 This test exemplifies the present invention and uses calcium carbonate tested in No. 5. The pour point after aging for 30 days at a temperature of 23 ° C in Formulation 1 was 102.1%, which was higher than the pour point of the No. 23 test.

Test No. 32 This test exemplifies the present invention and uses calcium carbonate tested in No. 6. The pour point after aging for 30 days at a temperature of 23 ° C in Formulation 1 was 36.4%, which was higher than the pour point of the No. 23 test.

Test No. 33 This test exemplifies the present invention and uses calcium carbonate tested in No. 7. The pour point after aging for 30 days at a temperature of 23 ° C in Formulation 1 was 4.2%, which was higher than the pour point of the No. 23 test.

Test No. 34 This test exemplifies the present invention and uses calcium carbonate tested in No. 8. The pour point after aging for 30 days at a temperature of 23 ° C in Formulation 1 was 86.7 %, which was higher than the pour point of the No. 23 test.

The results of all the above tests are reported in Table 1 below.

A satisfactory rheological result obtained from the product according to the invention can be seen by reading Table 1.

EXAMPLE 4 This example relates to the use of a pigment according to the invention as a rheology modifier for the preparation of a polyvinyl chloride (PVC) based plastisol and for the preparation of a variant different from that exemplified in Example 3. Formula.

In order to complete the present embodiment, a formulation 2 was produced in the same manner as in Example 3 and the same equipment.

This formulation 2 - a PVC-based plastisol - consists of -24% by weight of PVC resin Vestolit E 7031 ^{T M} (Vestolit, Germany), -6.0% by weight of PVC resin Vestolit C 65 ^{T M} ( Vestolit, Germany), -47.0% by weight of plasticizer DINP (diisononyl phthalate), -2.0% by weight of desiccant Super Weisskalk 40 (Omya AG, Switzerland), -1.0% by weight of adhesion promoter EURETEK 505 ^{T M} (Ciba SC, Switzerland), -20.0% by weight of inorganic pigment for testing.

For the various tests of the examples, the measurement of the viscosity and the pour point was carried out using the same operating conditions as the previous examples and the same equipment.

Test No. 35 This test is a prior art and uses precipitated calcium carbonate sold by the company Solvay under the trade name Winnofil SPT ^{T M.} This test is used as a reference.

Test No. 36 This test is a prior art and uses precipitated calcium carbonate sold by Solvay under the trade name Socal ^{T M} 322. The pour point after aging for 30 days at a temperature of 23 ° C in Formulation 2 was 108.3 %, which was higher than the pour point of the No. 35 test.

Test No. 37 This test exemplifies the prior art and uses calcium carbonate sold under the trade name Omyabond ^{T M} 302 by Omya Corporation. The pour point after aging for 30 days at a temperature of 23 ° C in Formulation 2 was 102.8 %, which was higher than the pour point of the No. 35 test.

Test No. 38 This test exemplifies the prior art and uses calcium carbonate sold under the trade name Omyabond ^{T M} 301 by Omya Corporation. The pour point after aging for 30 days at a temperature of 23 ° C in Formulation 2 was 58.3 %, which was lower than the pour point of the No. 35 test.

Test No. 39 This test illustrates the prior art and uses calcium carbonate from Test No. 2. The pour point after aging for 30 days at a temperature of 23 ° C in Formulation 2 was 275%, which was higher than the pour point of the No. 35 test.

Test No. 40 This test illustrates the invention and uses calcium carbonate tested No. 11. The pour point after aging for 30 days at a temperature of 23 ° C in Formulation 2 was 275%, which was higher than the pour point of the No. 35 test.

Test No. 41 This test exemplifies the present invention and uses calcium carbonate tested in No. 12. The pour point after aging for 30 days at a temperature of 23 ° C in Formulation 2 was 319.4%, which was higher than the pour point of the No. 35 test.

Test No. 42 This test exemplifies the present invention and uses calcium carbonate tested in No. 13. The pour point after aging for 30 days at a temperature of 23 ° C in Formulation 2 was 350 %, which was higher than the pour point of the No. 35 test.

Test No. 43 This test exemplifies the present invention and uses calcium carbonate tested in No. 14. The pour point after aging for 30 days at a temperature of 23 ° C in Formulation 2 was 422.2%, which was higher than the pour point of the No. 35 test.

All results for this example are reported in Table 2 below.

Reading Table 2 shows that the best rheological results are obtained from the product according to the invention.

EXAMPLE 5 This example relates to the use of a pigment according to the invention as a rheology modifier for the preparation of a polyvinyl chloride (PVC) based plastisol and for the preparation of one and the examples 3 and 4 Different formulations.

In order to complete the present embodiment, a formulation 3 was produced in the same manner as in Example 3 and the same equipment.

This formulation 3 - a PVC-based plastisol - consists of -31.0% by weight of PVC resin Vestolit E 7031 ^{T M} (Vestolit, Germany), -43.0% by weight of plasticizer DINP (o-phenylene) Diisononyl formate), -1.5% by weight of desiccant Super Weisskalk 40 (Omya AG, Switzerland), -1.0% by weight of adhesion promoter EURETEK 505 ^{T M} (Ciba SC, Switzerland), -1.0% by weight of heat stable Irgastab 17 M ^{T M} (Ciba SC, Switzerland), -22.5 wt% of inorganic pigment for testing.

For the various tests of the examples, the measurement of the viscosity and the pour point was carried out using the same operating conditions as the previous examples and the same equipment.

Test No. 44 This test illustrates the prior art and uses precipitated calcium carbonate sold under the trade name Winnofil SPT ^{T M} by Solvay. This test is used as a reference.

Test No. 45 This test is a prior art and uses precipitated calcium carbonate sold by Solvay under the trade name Socal ^{T M} 322. The pour point after aging for 30 days at a temperature of 23 ° C in Formulation 3 was 200%, which was higher than the pour point of the No. 44 test.

Test No. 46 This test exemplifies the prior art and uses calcium carbonate sold under the trade name Omyabond ^{T M} 302 by Omya Corporation. The pour point after aging for 30 days at a temperature of 23 ° C in Formulation 3 was 55.3%, which was lower than the pour point of the No. 44 test.

Test No. 47 This test exemplifies the prior art and uses calcium carbonate sold under the trade name Omyabond ^{T M} 301 by Omya Corporation. The pour point after aging for 30 days at a temperature of 23 ° C in Formulation 3 was 12.8%, which was higher than the pour point of the No. 44 test.

Test No. 48 This test exemplifies the present invention and uses calcium carbonate tested in No. 15. The pour point after aging for 30 days at a temperature of 23 ° C in Formulation 3 was 342.6 %, which was higher than the pour point of the No. 44 test.

Test No. 49 This test exemplifies the present invention and uses calcium carbonate tested in No. 16. The pour point after aging for 30 days at a temperature of 23 ° C in Formulation 3 was 712.8 %, which was higher than the pour point of the No. 44 test.

Test No. 50 This test exemplifies the present invention and uses calcium carbonate tested in No. 17. The pour point after aging for 30 days at a temperature of 23 ° C in Formulation 3 was 459.6 %, which was higher than the pour point of the No. 44 test.

Test No. 51 This test exemplifies the present invention and uses calcium carbonate tested in No. 18. The pour point after aging for 30 days at a temperature of 23 ° C in Formulation 3 was 740.4%, which was higher than the pour point of the No. 44 test.

The results of reading Table 3 show that by using a mixture of a fatty acid and a fatty alcohol or using only a fatty alcohol, we can also obtain satisfactory rheological results. Test No. 51 shows that the present invention can also be applied during the production of precipitated calcium carbonate.

Embodiment 6 This embodiment relates to the use of the pigment according to the present invention as a rheology modifier for preparing a polyvinyl chloride (PVC)-based plastisol, the formulation of the plastisol and the formulation of Example 5. It is different from the proportion of filler used for testing.

In order to complete the present embodiment, a formulation 4 was produced in the same manner as in Example 3 and the same equipment.

This formulation 4-PVC-based plastisol is composed of -31.0% by weight of PVC resin Vestolit E 7031 ^{T M} (Vestolit, Germany), -43.0% by weight of plasticizer DINP (o-phenylene) Diisononyl formate), -1.5% by weight of desiccant Super Weisskalk 40 (Omya AG, Switzerland), -1.0% by weight of adhesion promoter EURETEK 505 ^{T M} (Ciba SC, Switzerland), -1.0% by weight of heat stable Irgastab BZ 529 ^{T M} (Ciba SC, Switzerland), -15.0% to 22.5% by weight of test inorganic pigment.

For the various tests of the examples, the measurement of the viscosity and the pour point was carried out using the same operating conditions as the previous examples and the same equipment.

Test No. 52 This test illustrates the prior art and uses 22.5% of precipitated calcium carbonate sold by Solvay Corporation under the trade name Winnofil SPT ^{T M.} This test is used as a reference.

Test No. 53 This test illustrates the prior art and uses 22.5% of precipitated calcium carbonate sold by Solvay Corporation under the trade name Socal ^{T M} 322. The pour point after aging for 30 days at a temperature of 23 ° C in Formulation 4 was 42%, which was higher than the pour point of the No. 52 test.

Test No. 54 This test illustrates the invention and uses 20.0% of the calcium carbonate tested No. 21.

Test No. 55 This test illustrates the invention and uses 15.0% of the calcium carbonate tested No. 21.

Test No. 56 This test illustrates the invention and uses 20.0% of the calcium carbonate tested No. 22.

Test No. 57 This test illustrates the invention and uses 15.0% of the calcium carbonate tested No. 22.

All results for this example are reported in Table 4 below.

Reading Table 4 above, it can be observed that the use of the pigments according to the invention allows the plastisol to achieve the same pour point to reduce the inorganic filler by about at least 33%, which reduces the weight of the filled plastisol.

EXAMPLE 7 This example illustrates the invention and relates to the use of the pigment according to the invention (made of rigid PVC (hard polyvinyl chloride)), such as a frame of an automobile body, which retains the control of firmness while From the point of view of reducing weight.

In the various tests of the examples, it was tested to replace the prior art calcium carbonate with the inorganic pigments according to the invention.

In a rigid PVC formulation, attempts were made to compare the effects of the inorganic fillers of the prior art with 100% of the inorganic pigments according to the present invention.

To complete this test, the tensile properties of the following rigid PVC formulations were measured (which is a measure of firmness for those skilled in the art): -100 phr. of rigid PVC resin EVDPOLSH 6521 (EVC, Germany), -1.5 phr. The trivalent lead sulfate heat stabilizer Naftorin T 3 (Chemson, UK), -1.5 phr. of the dibasic lead sulfate heat stabilizer Listab 51 (Chemson, UK), -0.6 phr. of the lubricant Ca F 1 (Hoechst, Germany), -0.05 phr of lubricant E-Wachs (Hoechst, Germany), -30 phr. of inorganic pigment for testing.

The rigid PVC resin and the inorganic filler were mixed in a two-roll mill (Collin, model 150x400) at a temperature of 190 °C. After pressing into a plate shape at 190 ° C to shape, the rigid PVC sheet was ground (Collin, model P 300 P).

The samples for tensile testing were formed from the sheet according to DIN 53 455. The tensile resistance was measured using a "Zwick/Roell" ^{T M} Z020 instrument and on a DIN 53 455 basis.

Test No. 58 This test illustrates the prior art and uses precipitated calcium carbonate sold by the company Solvay under the trade name Winnofil SPT ^{T M.} This test is for reference.

Test No. 59 This test is a prior art and uses precipitated calcium carbonate sold by Solvay under the trade name Socal ^{T M} 322.

The same tensile resistance as Winnofil SPT ^{T M was} produced using Socal ^{T M} 322.

Test No. 60 This test exemplifies the prior art and uses calcium carbonate sold under the trade name of Hydrocarb ^{T M} 120T by Omya Corporation. Hydrobel ^{T M} 120T was used to produce the same tensile resistance as Winnofil SPT ^{T M.}

Test No. 61 This test exemplifies the prior art and uses calcium carbonate sold under the trade name Omyabond ^{T M} 301 by Omya Corporation.

The same tensile resistance as Winnofil SPT ^{T M was} produced using Omyabond ^{T M} 301.

EXAMPLE 8 This example illustrates the invention and is related to the inorganic pigments according to the invention (tests Nos. 62, 63, 64 and 65), the method of manufacture according to the invention (tests 62, 63, 64 and 65) And its use in the plastisol-based PVC formulation according to the invention (tests Nos. 63, 64 and 65).

Test No. 62 This test is illustrative of the present invention and relates to a process for obtaining a pigment according to the present invention, in which a treatment with a 1% fatty acid mixture occurs before the reaction of marble-type calcium carbonate with phosphoric acid.

To complete this test, 6,974 kg (by dry weight of pigment) was used as an aqueous suspension (with a dry content of 78%, dispersed with 0.5% sodium polyacrylate) in a 10 liter ESCO ^{T M} reactor using distilled water. , a natural type of calcium carbonate of Norwegian marble type (using a particle size analysis measured by Sedigraph ^{T M} 5100 of Micromeritics ^{T M} Company, having a diameter of 65% by weight of the particles having a diameter of less than 1 μm) is diluted until a dry matter having 65 wt% is obtained. Aqueous suspension.

Then in a suspension of 1% fatty acid (present in sunflower oil, with palmitic acid, stearic acid, oleic acid, linoleic acid and linoleic acid at the temperature equal to 70 ° C, CAS number is equal to 67701-08 -0) The suspension thus formed is treated.

After stirring for 5 minutes, the suspension thus formed was treated with 1% phosphoric acid (10% by weight solution) during stirring for 30 minutes.

After the addition of 94 grams of 14% by weight calcium hydroxide, the suspension had a pH equal to 8.6 and a dry solids content percentage equal to 62.2%.

The suspension thus obtained was dried at 80 ° C using a Nara ^{T M} MSD-100 dryer. Thus, an inorganic pigment according to the invention is obtained.

Test No. 63 This test is illustrative of the present invention and relates to a process for obtaining a pigment according to the present invention, in which a treatment with a 1% fatty acid mixture occurs after the reaction of marble-type calcium carbonate with phosphoric acid.

To complete this test, 0,707 kg (by dry weight of pigment) was used as an aqueous suspension (with a dry content of 78%, dispersed with 0.5% sodium polyacrylate) in a 10 liter ESCO ^{T M} reactor using distilled water. , Norwegian marble type natural calcium carbonate (particle size analysis measured by Sedigraph 5100 of Micromeritics ^{T M} Company is 65% by weight of the particle system having a diameter of less than 1 μm) is diluted until an aqueous suspension having 65% by weight of dry matter is obtained .

The suspension thus formed was then treated with 50% phosphoric acid (10% by weight solution) at a temperature equal to 70 ° C for 30 minutes.

Then, a 1% fatty acid composed of palmitic acid and stearic acid in a ratio of 1/1 by weight was added as a powder.

After the addition of 135 grams of 14% by weight calcium hydroxide, the suspension has a pH equal to 8.1 and a dry solids content percentage equal to 7.5%.

The suspension thus obtained was used based Nara ^{T M} MSD-100 drier at 80 ℃.

A plastisol-like PVC formulation is then prepared comprising -33% by weight of Vestolit ^{T M} E 7031, 44% diisodecyl phthalate, 1,6 % Weisskalk ^{T M} Super 40. ¹ % Euretek ^{T M} 505 and 20% of the previously obtained inorganic pigment according to the invention.

The drop point of this composition - measured after 72 hours according to methods well known to those skilled in the art - is equal to 548 Pa.

Test No. 64 This test is illustrative of the present invention and relates to a process for obtaining a pigment according to the present invention, in which a treatment with a 0,5 % fatty acid mixture occurs in the reaction of marble-like calcium carbonate with phosphoric acid. after that.

To complete this test, 0,698 kg (by dry weight of pigment) was used as an aqueous suspension in a 10 liter ESCO ^{T M} reactor (dry matter content 78%, dispersed with 0.5% sodium polyacrylate) , Norwegian marble type natural calcium carbonate (particle size analysis measured by Sedigraph 5100 of Micromeritics ^{T M} Company is 65% by weight of the particle system having a diameter of less than 1 μm) is diluted until an aqueous suspension having 65% by weight of dry matter is obtained .

The thus formed suspension was then treated with a mixed solution of 50% phosphoric acid and sulfuric acid (10% by weight solution) at a temperature equal to 70 ° C for 60 minutes.

Then, in suspension, 0,5 % fatty acids (present in linseed oil, having the following composition by weight: 8 % fatty acids having 12 to 16 carbon atoms, 3% stearic acid, 19% oleic acid) The resulting suspension was treated with 16% linoleic acid and 52% linoleic acid and 2% acid having 20 to 22 carbon atoms.

After the addition of 250 grams of 14% by weight calcium hydroxide, the suspension has a pH equal to 8.1 and a dry solids content percentage equal to 7.55%.

The suspension thus obtained was dried at 80 ° C using a Nara ^{T M} MSD-100 dryer.

A plastisol-like PVC formulation is then prepared comprising -35,4% by weight of Vestolit ^{T M} E 7031, 46, 8% of diisononyl phthalate, 1,7 % of Weisskalk ^{T M} Super 40, 1, 1% Euretek ^{T M} 505 and 15% of the previously obtained inorganic pigments according to the invention.

The pour point of this composition - measured after 72 hours according to methods well known to those skilled in the art - is equal to 510 Pa.

Test No. 65 This test is illustrative of the present invention and relates to a process for obtaining a pigment according to the present invention, in which a treatment with a mixture of 0,2% fatty acid occurs in the reaction of marble-like calcium carbonate with phosphoric acid. after that.

To complete this test, 0,694 kg (by dry weight of pigment) was used as an aqueous suspension in a 10 liter ESCO ^{T M} reactor (dry matter content 78%, 0,77% sodium polyacrylate) dispersion), the type of natural Norwegian marble calcium carbonate (the company using Micromeritics ^{T M} measured by Sedigraph 5100 particle size analyzer having a diameter of less than 1μm) was diluted to 65% by weight based particles, until 65 wt% aqueous having a dry matter suspension.

The suspension thus formed was then treated with a 10% phosphoric acid and sulfuric acid mixture (10% by weight solution) at a temperature equal to 70 ° C for 30 minutes.

Then, as a suspension of 2% fatty acid (present in coconut oil, stearic acid, an acid having 10 carbon atoms, an acid having 12 carbon atoms, an acid having 14 carbon atoms, palmitic acid, having A suspension of 20 to 22 carbon atoms of acid, mainly CAS number equal to 67701-05-7).

After the addition of 136 grams of 14% by weight calcium hydroxide, the suspension has a pH equal to 9,7 and a dry solids content percentage equal to 10,1%.

The suspension thus obtained was dried at 80 ° C using a Nara ^{T M} MSD-100 dryer.

A plastisol-like PVC formulation is then prepared comprising -25% by weight of Vestolit ^{T M} E 7031, 33,0% diisononyl phthalate, 1,2% Weisskalk ^{T M} Super 40, 0, 8 % of Euretek ^{T M} 505 and 40,0% of the previously obtained inorganic pigments according to the invention.

The point of drop of this composition - measured after 72 hours according to methods well known to those skilled in the art - is equal to 502 Pa.

Claims (125)

A dry inorganic pigment characterized in that the dry inorganic pigment contains a product formed in situ by a multiple reaction between calcium carbonate and the following: - the calcium carbonate and one or more medium strength to strong H3O ⁺ ion supply reaction product reaction product of one or more persons; - and the calcium carbonate formed in situ and / or originating from an external supply of the gaseous reaction products CO ₂ or more reaction products; - one or more compounds having the formula RX, wherein The R group of the compound of the formula RX or the plurality of compounds represents a carbon-containing group having 8 to 24 carbon atoms whether or not saturated, and is characterized by the compound of the formula RX or a plurality of compounds The X group represents a group of a carboxylic acid group, an amine group, a hydroxyl group, a phosphonic acid group or a mixture thereof. A dry inorganic pigment according to claim 1 wherein R is a linear or branched alkyl, alkaryl, aralkyl, aryl, polyaryl or cyclic group or a mixture thereof. . The dry inorganic pigment according to the first aspect of the patent application, characterized in that the compound of the formula RX is selected from a fatty acid, an aliphatic amine or an aliphatic alcohol, whether saturated or a mixture thereof, or Mixture with synthetic or natural aliphatic compounds. A dry inorganic pigment according to claim 3, wherein the compound of the formula R-X has 8 to 24 carbon atoms. The dry inorganic pigment according to item 3 of the patent application, wherein the compound of the formula R-X is selected from the group consisting of stearic acid, oleic acid, linoleic acid, myristic acid, and octanoic acid. A dry inorganic pigment according to claim 3, wherein the compound of the formula R-X has 16 to 18 carbon atoms. A dry inorganic pigment according to item 3 of the patent application, wherein the synthetic or natural aliphatic compound is a compound of vegetable or animal origin. A dry inorganic pigment according to item 7 of the patent application, wherein the vegetable source is coconut oil. A dry inorganic pigment according to item 7 of the patent application, wherein the animal source is butter. A dry inorganic pigment according to item 7 of the patent application, wherein the synthetic or natural aliphatic compound is a compound of vegetable origin. The dry inorganic pigment according to any one of claims 1 to 10, wherein the medium strength to strong H3O+ ion donor is selected from a medium strong acid to strong acid which produces H ₃ O ⁺ ions or A mixture of acids. The scope of the patent the dry inorganic pigment, Paragraph 11, wherein the acid has less than or equal to 2.5 when the pK _a of moderate to strong H3O ⁺ ion providers selected based at 25 ℃. The scope of the patent the dry inorganic pigment, Paragraph 11, wherein the plurality of strong acid or a strong acid having an acid-based or equal to 0 less than the pK _a time selected from 25 ℃. A dry inorganic pigment according to claim 13 wherein the strong acid or the plurality of strong acids are selected from the group consisting of sulfuric acid, hydrochloric acid or a mixture of such acids. The scope of the patent the dry inorganic pigment, Paragraph 11, characterized in that the medium-strong acid or strong acid-based medium having a plurality of between 0 and 2.5 and 2.5 comprising the pK _a of the acid is selected from the time 25 ℃. The dry inorganic pigment according to claim 15 wherein the medium strong acid or the plurality of medium strong acids are selected from the group consisting of H ₂ SO ₃ , HSO ₄ ^- , H ₃ PO ₄ or a mixture of such acids. The dry inorganic pigment according to claim 15 of the patent application, characterized in that the medium strong acid or the plurality of medium strong acids are selected from medium strong acids which form divalent cation salts, and the salts are hardly soluble in water, that is, Only has a solubility of less than 1% by mass. A dry inorganic pigment according to item 17 of the patent application, wherein the divalent cation is calcium. The inorganic pigment according to any one of claims 1 to 10, characterized in that the calcium carbonate is a natural calcium carbonate. The inorganic pigment according to claim 19, wherein the natural calcium carbonate is selected from the group consisting of marble, calcite, chalk, limestone or a mixture thereof. The dry inorganic pigment according to any one of claims 1 to 10, characterized in that the dry inorganic pigment has a difference between 1 m ² /g and 200 m ² /g as measured according to the BET method. the specific surface area (specific surface area) is between 0.1 and 50 microns and a median diameter of 5100 measured using Sedigraph ^TM measured. The dry inorganic pigment according to claim 21, wherein the dry inorganic pigment has a specific surface area of between 5 m ² /g and 80 m ² /g as measured according to the BET method. The dry inorganic pigment according to claim 21, wherein the dry inorganic pigment has a specific surface area of between 20 m ² /g and 60 m ² /g as measured according to the BET method. The patentable scope of dry application of 21 of an inorganic pigment, characterized in that the dry inorganic pigment system having a median diameter of between 1 and 10 microns measured using a Sedigraph ^TM 5100 of the assay. The dry inorganic pigment according to any one of claims 1 to 10, wherein the moisture ratio is less than 1.50%, which is measured when the moisture ratio is dried at 120 ° C for 2 hours in an oven at atmospheric pressure. . A method of producing a dry inorganic pigment comprising a product formed in situ from a multiple reaction between calcium carbonate and one or more medium to strong H3O+ ion donors a reaction product or a plurality of reaction products, and a reaction product or a plurality of reaction products of the calcium carbonate and in situ formed and/or derived from externally supplied gaseous CO ₂ , and one or more compounds of the formula RX, the chemical formula The R-based compound or the R-based group of the plurality of compounds represents a carbon-containing group having 8 to 24 carbon atoms whether or not saturated, and the X group represented by the compound of the formula RX or a plurality of compounds a group of a carboxylic acid group, an amine group, a hydroxyl group, a phosphonic acid group or a mixture thereof, characterized in that the method comprises the following stages: a) treating the carbonic acid in the aqueous phase with a medium strength to strong H3O+ ion donor. to calcium and gaseous CO ₂ formed in situ process, this is a process stage a) the essential part, b) to one or more classes of compound RX compound-treated calcium carbonate in the aqueous phase, the point having the formula RX, wherein The compound or compounds are added before and/or during and/or after stage a), c) anionic or cationic of the product obtained in stage b) which may form a dry matter concentration between 1% and 80% Or a weak anionic aqueous suspension, it is possible to use at least one anionic or cationic or weak anionic electrolyte, and then may be followed by repeated concentration, d) may add a base in order to increase the pH to above 6, e ) drying after one of the stages b), c) or d). A method of producing a dry inorganic pigment according to claim 26, wherein the base is Ca(OH) ₂ . A method of producing a dry inorganic pigment according to claim 26, wherein the pH is increased to a value of 7.5 or more. A method of producing a dry inorganic pigment according to claim 26, wherein the pH is increased to a value between 8 and 10. The method for producing a dry inorganic pigment according to claim 26, wherein the R group is a linear or branched alkyl group, an alkylaryl group, an aralkyl group, an aryl group, a polyaryl group or a cyclic group or These mixtures. The method for producing a dry inorganic pigment according to claim 26, wherein the compound of the formula RX is selected from a fatty acid, an aliphatic amine or an aliphatic alcohol, whether saturated or a mixture thereof. Or a mixture of them with synthetic or natural aliphatic compounds. A method of producing a dry inorganic pigment according to claim 31, wherein the compound of the formula R-X has 8 to 24 carbon atoms. The method for producing a dry inorganic pigment according to claim 31, wherein the compound of the formula R-X is selected from the group consisting of stearic acid, oleic acid, linoleic acid, myristic acid, and octanoic acid. A method of producing a dry inorganic pigment according to claim 31, wherein the compound of the formula R-X has 16 to 18 carbon atoms. A method of producing a dry inorganic pigment according to claim 31, wherein the synthetic or natural aliphatic compound is a compound of a vegetable or animal origin. A method of producing a dry inorganic pigment according to claim 35, wherein the vegetable source is coconut oil. A method of producing a dry inorganic pigment according to claim 35, wherein the animal source is butter. A method of producing a dry inorganic pigment according to claim 35, wherein the synthetic or natural aliphatic compound is a vegetable-derived compound. A method of producing a dry inorganic pigment according to any one of claims 26 to 38, characterized in that the calcium carbonate is a natural calcium carbonate. A method of producing a dry inorganic pigment according to claim 39, wherein the natural calcium carbonate is selected from the group consisting of marble, calcite, chalk, limestone or a mixture thereof. The method for producing a dry inorganic pigment according to any one of claims 26 to 38, wherein the medium strength to strong H3O ⁺ ion donor is selected from a medium strong acid which produces H ₃ O ⁺ ions. Strong acid or a mixture of such acids. The method of producing a range of patent application 41 of the dry inorganic pigment, an acid having less than or equal to 2.5 when the pK _a of moderate to strong H3O ⁺ ion providers selected based at 25 ℃. The method of producing a range of patent application 41 of the dry inorganic pigment, wherein the plurality of strong acid or a strong acid having an acid based 0 less than or equal to the pK _a time selected from 25 ℃. A method of producing a dry inorganic pigment according to claim 43 wherein the strong acid or the plurality of strong acids are selected from the group consisting of sulfuric acid, hydrochloric acid or a mixture of such acids. The method of producing a range of patent application 41 of the dry inorganic pigment, characterized in that the medium-strong acid or strong acid-based medium having a plurality of between 0 and 2.5 and 2.5 comprising the pK _a of the acid is selected from the time 25 ℃. A method of producing a dry inorganic pigment according to claim 45, wherein the medium strong acid or the plurality of medium strong acids are selected from the group consisting of H ₂ SO ₃ , HSO ₄ ^- , H ₃ PO ₄ or a mixture of such acids. The method for producing a dry inorganic pigment according to claim 44, wherein the medium strong acid or the plurality of medium strong acids are selected from medium strong acids which form divalent cation salts, and the salts are hardly soluble in water. That is, it has only a solubility of less than 1% by mass. A method of producing a dry inorganic pigment according to claim 47, wherein the divalent cation is calcium. A method of producing a dry inorganic pigment according to any one of claims 26 to 38, characterized in that the strong acid or a plurality of strong acids are compatible with the Medium strong acid or a mixture of medium and strong acids. The method for producing a dry inorganic pigment according to any one of claims 26 to 38, characterized in that the molar component of the medium strength to strong H3O ⁺ ion supplier is a total of the molar number of CaCO ₃ Between 0.001 and 1. A method of producing a dry inorganic pigment according to claim 50, wherein the molar component of the medium strength to strong H3O ⁺ ion donor is between 0.1 and 0.5 with respect to the molar number of CaCO ₃ . The method for producing a dry inorganic pigment according to any one of claims 26 to 38, wherein the molar component of the plurality of compounds of the formula RX is 0.0001 in relation to the molar number of CaCO ₃ . Between 0.1 and 0.1. A method of producing a dry inorganic pigment according to claim 52, wherein the molar component of the plurality of compounds of the formula RX is between 0.002 and 0.01 in total with respect to the molar number of CaCO ₃ . The method for producing a dry inorganic pigment according to any one of claims 26 to 38, wherein the stage a) is repeatable several times, and the order of addition of the medium strong acid and the strong acid is to a medium strong acid or It is not important to add before and/or during the strong acid and/or after. A method of producing a dry inorganic pigment according to any one of claims 26 to 38, characterized in that the stage b) can be repeated several times. A method of producing a dry inorganic pigment according to any one of claims 26 to 38, characterized in that the temperature during the stage a) of the treatment is between 5 ° C and 100 ° C. A method of producing a dry inorganic pigment according to claim 56, wherein the temperature during the period a) of the treatment is between 65 ° C and 80 ° C. The method of producing a dry inorganic pigment according to any one of claims 26 to 38, characterized in that the duration of the treatment stage a) lasts between 0.01 hours and 10 hours. A method of producing a dry inorganic pigment according to claim 58 of the patent application, wherein the duration of the treatment stage a) is between 0.2 hours and 6 hours. A method of producing a dry inorganic pigment according to any one of claims 26 to 38, characterized in that the method is carried out in an aqueous phase of a dilute, ordinary concentrated or concentrated dry matter concentration. A method of producing a dry inorganic pigment according to claim 60, wherein the dry matter content is between 1% by weight and 80% by weight. A method of producing a dry inorganic pigment according to any one of claims 26 to 38, characterized in that the stage c) uses 0.01% by dry weight to 5.0% by dry weight of an anionic electrolyte selected from the following a homopolymer or copolymer composed of monomers and in a state of being unneutralized, partially neutralized or all neutralized: a monomer having an ethylenic unsaturation and having a monocarboxylic acid function, or Is a diacid half ester, or a mixture thereof or the like, or a monomer having a dicarboxylic acid function selected from a monomer having an ethylenic unsaturation and having a dicarboxylic acid function, or the same An acid anhydride, or a monomer having a sulfonic acid function, which is selected from a monomer having an ethylenic unsaturation and having a sulfonic acid function, or a monomer having a phosphoric acid function, Is selected from a monomer having an ethylenic unsaturation and having a phosphoric acid function, or a monomer having a phosphonic acid function, which is selected from a monomer having an ethylenic unsaturation and having a phosphonic acid function. Or a mixture thereof or a polyphosphate. A method of producing a dry inorganic pigment according to claim 62, wherein the monomer having an ethylenic unsaturation and having a monocarboxylic acid function is acrylic acid or methacrylic acid. A method of producing a dry inorganic pigment according to claim 62, wherein the diacid half ester is a C ₁ to C ₄ monoester of maleic acid or itaconic acid. A method for producing a dry inorganic pigment according to the scope of claim 62, wherein the monomer having an ethylenic unsaturation and having a dicarboxylic acid function is crotonic acid, isocrotonic acid, cinnamic acid, isaconic acid or malay acid. A method of producing a dry inorganic pigment according to claim 62, wherein the acid anhydride of the carboxylic acid is maleic anhydride. A method for producing a dry inorganic pigment according to claim 62, wherein the monomer having an ethylenic unsaturation and having a sulfonic acid function is acrylamide-methyl-propane-sulfonic acid, methyl allylate Sodium sulfonate, ethylenesulfonic acid and styrene sulfonic acid. The method for producing a dry inorganic pigment according to claim 62, wherein the monomer having an ethylenic unsaturation and having a phosphoric acid function is ethylene phosphate, ethylene glycol (methacrylate) phosphate, propylene glycol (A) Phosphate esters, ethylene glycol (acrylate) phosphates, propylene glycol (acrylate) phosphates, and such ethoxylates. Production of dry inorganic pigments according to Article 62 of the patent application The method wherein the monomer having an ethylenic unsaturation and having a phosphonic acid function is a vinylphosphonic acid. A method of producing a dry inorganic pigment according to any one of claims 26 to 38, characterized in that the stage c) uses a cationic electrolyte between 0.01% by dry weight and 5.0% by dry weight, which is selected From homopolymers or copolymers of cationic monomers or quaternary ammonium having ethylenic unsaturation. A method for producing a dry inorganic pigment according to claim 70, wherein the quaternary ammonium [2-(methacryloxy)ethyl]trimethylammonium chloride or [2-(methacryloxime) Oxy)ethyl]ammonium trimethylammonium sulfate, [2-(acryloxy)ethyl]trimethylammonium chloride or [2-(acryloxy)ethyl]trimethylammonium sulfate, [ 3-(Propylguanidino)propyl]trimethylammonium chloride or [3-(acrylamido)propyl]trimethylammonium sulfate, dimethyldiallylammonium chloride or dimethyl Ammonium ammonium sulfate or [3-(methacryl oxime) propyl]trimethylammonium chloride or [3-(methacrylamido)propyl]trimethylammonium sulfate. The method for producing a dry inorganic pigment according to any one of claims 26 to 38, wherein the stage c) is a weak anionic electrolyte having a dry weight of from 0.01% to 5.0%, a water-soluble copolymer selected from the group consisting of weakly ionic, comprising: a) at least one anionic monomer having a carboxylic acid or a dicarboxylic acid or a phosphoric acid or a phosphonic acid or a sulfonic acid function, or a mixture thereof, b) at least one non An ionic monomer, wherein the nonionic single system is composed of at least one monomer of formula (I): (wherein: m and p represent the number of alkylene oxide units less than or equal to 150, n represents the number of ethylene oxide units less than or equal to 150, and q represents an integer at least equal to 1 such that 5 (m+n+p)q 150R1 represents hydrogen or methyl or ethyl, R2 represents hydrogen or methyl or ethyl, R represents a group containing an unsaturated polymerizable function, and R' represents hydrogen or a hydrocarbon group having 1 to 40 carbon atoms. Or a mixture of a plurality of monomers of formula (I), c) at least one acryloylguanamine or methacrylamide amine or a derivative thereof, and mixtures thereof Is at least one water-insoluble monomer, unsaturated ester, ethylene, and the like, or at least one cationic monomer or quaternary ammonium, or at least one organic fluorinated monomer or organic deuterated single The body, or a mixture of several such monomers, d) may be at least one monomer having at least two ethylenic unsaturations referred to as grafting monomers. A method of producing a dry inorganic pigment according to claim 72, wherein q represents an integer at least equal to 1 such that 15 (m+n+p)q 120. Production of dry inorganic pigments according to Article 72 of the patent application a method, wherein R is an ethylene group, or is an acrylate, methacrylate, maleate, isoconate, crotonate, vinyl phthalate, or an unsaturated urethane, or Allyl ether or vinyl ether, whether or not substituted, is either an ethylenically unsaturated decylamine or a quinone imine. A method for producing a dry inorganic pigment according to claim 74, wherein the unsaturated urethane is acryloyl methacrylate, methacryl decyl urethane, α-α' dimethyl Base-isopropenyl-benzylaminocarbamate, allyl carbazate. A process for producing a dry inorganic pigment according to claim 72, wherein R' represents a hydrocarbon group having 1 to 12 carbon atoms. A method of producing a dry inorganic pigment according to claim 72, wherein R' represents a hydrocarbon group having 1 to 4 carbon atoms. A method for producing a dry inorganic pigment according to the scope of claim 72, wherein the propylene decyl decylamine or methacryl oxime amide monomer or the derivative is N-[3-(dimethylamine) Base) propyl]propenyl decylamine or N-[3-(dimethylamino)propyl]methacrylinylguanamine. A method of producing a dry inorganic pigment according to claim 72, wherein the water-insoluble monomer is an alkyl acrylate or a methacrylate. A method for producing a dry inorganic pigment according to claim 72, wherein the unsaturated ester is N-[2-(dimethylamino)ethyl]methacrylate or N-[2-(dimethyl Amino) ethyl] acrylate. Production of dry inorganic pigments according to Article 72 of the patent application The method wherein the ethylene is vinyl acetate, vinyl pyrrolidone, styrene, α-methyl styrene. A method for producing a dry inorganic pigment according to claim 72, wherein the cationic monomer or quaternary ammonium is [2-(methacryloxy)ethyl]trimethylammonium chloride or [2- (Methethyloxy)ethyl]trimethylammonium sulfate, [2-(acryloxy)ethyl]trimethylammonium chloride or [2-(acryloxy)ethyl]trimethyl Ammonium sulfate, [3-(acrylamido)propyl]trimethylammonium chloride or [3-(acrylamido)propyl]trimethylammonium sulfate, dimethyldiallyl chloride Ammonium or dimethyldiallylammonium sulfate or [3-(methacrylamidino)propyl]trimethylammonium chloride or [3-(methacrylamidido)propyl]trimethyl Ammonium sulfate. A dry inorganic pigment comprising a product formed in situ from a multiplex reaction between calcium carbonate and one or more intermediate or strong H3O+ ion donors or a plurality of reaction products, And a reaction product or a plurality of reaction products of the carbonate and in situ formed and/or derived from externally supplied gaseous CO ₂ , and one or more compounds of the formula RX, characterized in that the dry inorganic pigment is Obtained by the method of any one of claims 26 to 82. Dry inorganic pigment according to item 83 of the patent application, characterized in that the dry inorganic pigment has a specific surface area of between 1 m ² /g and 200 m ² /g as determined by the BET method ISO 9277 and is used by Sedigraph ^TM 5100 measuring range of the measured median diameter of between 0.1 and 50 microns. A dry inorganic pigment according to claim 84, wherein the dry inorganic pigment has a specific surface area of between 5 m ² /g and 80 m ² /g as determined according to BET method ISO 9277. A dry inorganic pigment according to the invention of claim 84, wherein the dry inorganic pigment has a specific surface area of between 20 m ² /g and 60 m ² /g as determined according to the BET method ISO 9277. The scope of the patent the dry inorganic pigment, Paragraph 84, wherein the dry-based inorganic pigment having a median diameter of between 1 and 10 [mu] m measured using the Sedigraph ^TM 5100 of the assay. An aqueous suspension of an inorganic pigment obtained by stages c) to d) of the method according to any one of claims 26 to 69, characterized in that the inorganic pigment has a BET method (ISO) 9277) measured between 1 m ² / g and a specific surface area between ² / g 200 m and the median diameter is between 0.1 and 50 microns measured by Sedigraph ^TM 5100 using the measured, and in that The suspension has a dry matter content of between 1% and 80%, and in that the aqueous inorganic pigment suspension contains between 0.05% and 5.0% by dry weight relative to the dry weight of calcium carbonate. At least one anionic electrolyte. An aqueous inorganic pigment suspension according to claim 88, wherein the inorganic pigment has a specific surface area of between 5 m ² /g and 80 m ² /g as determined by the BET method (ISO 9277). An aqueous inorganic pigment suspension according to claim 88, wherein the inorganic pigment has a specific surface area of between 10 m ² /g and 60 m ² /g as determined by the BET method (ISO 9277). The scope of the patent application 88 of an aqueous suspension of inorganic pigment, wherein the inorganic pigment system having a median diameter between 1 and 10 microns measured using a Sedigraph ^TM 5100 of the assay. The aqueous inorganic pigment suspension according to any one of the preceding claims, wherein the anionic electrolyte is selected from the anionic electrolyte according to any one of claims 62 to 69. An aqueous suspension of inorganic pigment obtained according to stages c) to d) of the method of any one of claims 26 to 61 and 70-71, characterized in that the inorganic pigment has a use BET method (ISO 9277) measured between 1 m ² / g and a specific surface area between ² / g 200 m, and a median of 5100 measured using Sedigraph ^TM measured between 0.1 and 50 microns The diameter, and in that the suspension has a dry matter content between 1% and 80%, and in that the suspension contains between 0.1% and 5.0% by dry weight relative to the dry weight of calcium carbonate. At least one cationic electrolyte between. An aqueous inorganic pigment suspension according to claim 93, wherein the inorganic pigment has a specific surface area of between 5 m ² /g and 80 m ² /g as measured by the BET method (ISO 9277). An aqueous inorganic pigment suspension according to claim 93, wherein the inorganic pigment has a specific surface area of between 20 m ² /g and 60 m ² /g as measured by the BET method (ISO 9277). The scope of the patent an aqueous suspension of the inorganic pigment of 93, wherein the inorganic-based pigment having a median diameter using between 1 and 10 microns as measured Sedigraph ^TM 5100 of measurement. An aqueous inorganic pigment suspension according to any one of claims 93 to 96, wherein the cationic electrolyte is selected from the group consisting of A cationic electrolyte according to any one of claims 70 to 71. An aqueous suspension of an inorganic pigment obtained according to stages c) to d) of the method of any one of claims 26 to 82, characterized in that the inorganic pigment has a BET method (ISO 9277). measured between 1 m ² / g using the BET method of between ² / g 200 m measured specific surface area and the median is between 0.1 and 50 microns measured by Sedigraph ^TM 5100 using the measured a number of diameters, and in that the suspension has a dry matter content between 0.3% and 80%, and in that the suspension contains between 15% and 60 dry weights relative to the dry weight of calcium carbonate. At least one weak anionic electrolyte between %. An aqueous suspension of an inorganic pigment according to claim 98, wherein the inorganic pigment has a BET method of between 5 m ² /g and 80 m ² /g as measured by a BET method (ISO 9277) The measured specific surface area. An aqueous suspension of an inorganic pigment according to claim 98, wherein the inorganic pigment has a BET method of between 20 m ² /g and 60 m ² /g as measured by a BET method (ISO 9277) The measured specific surface area. The patentable scope of application of the inorganic pigment 98 of an aqueous suspension, wherein the inorganic-based pigment having a median diameter of between 1 and 10 [mu] m measured using the Sedigraph ^TM 5100 of the assay. The aqueous inorganic pigment suspension according to any one of claims 98 to 101, wherein the weak anionic electrolyte is selected from the weak anionic property according to any one of claims 72 to 82 of the patent application. Electrolyte. A use of a dry inorganic pigment according to any one of claims 1 to 25 and 83 to 87 as a method for adjusting a plastisol formulation and a rigid polyvinyl chloride (PVC) formulation Rheological filler. The use of a dry inorganic pigment according to claim 103 of the patent application, wherein the use is as a filler which allows the viscosity of the plastisol formulation and the rigid PVC formulation to be maintained while the viscosity is controlled. The use of a dry inorganic pigment according to any one of claims 103 to 104, which is used in the automotive industry. According to the use of the dry inorganic pigment of claim 105, it is used for the underbody protection covering. A use of a dry inorganic pigment according to any one of claims 1 to 25 and 83 to 87 in the field of paints and/or high build coatings and/or coatings. An aqueous inorganic pigment suspension according to any one of claims 88 to 102, which is used as a filler for adjusting a plastisol formulation and a rigid polyvinyl chloride (PVC) formulation. . According to the use of the aqueous suspension of inorganic pigments of claim 108, the use is as a filler which allows the viscosity of the plastisol formulation and the rigid PVC formulation to be maintained while the viscosity is controlled. The use of an aqueous inorganic pigment suspension according to any one of claims 108 to 109, which is used in the automotive industry. Aqueous suspension of inorganic pigments according to Article 110 of the patent application The use of liquid for the underbody protection covering. An use of an aqueous suspension of an inorganic pigment according to any one of claims 88 to 102 in the field of paints and/or high build coatings and/or coatings. A plastisol formulation, characterized in that the plastisol formulation contains a dry inorganic pigment according to any one of claims 1 to 25 and 83 to 87. A plastisol formulation, characterized in that the plastisol formulation contains an aqueous suspension of an inorganic pigment according to any one of claims 88 to 102. A rigid PVC formulation, characterized in that the rigid PVC formulation contains a dry inorganic pigment according to any one of claims 1 to 25 and 83 to 87. A rigid PVC formulation characterized in that the rigid PVC formulation contains an aqueous suspension of an inorganic pigment according to any one of claims 88 to 102. A underbody protective covering material characterized by comprising a dry inorganic pigment according to any one of claims 1 to 25 and 83 to 87 in a portion between 0.05% and 50%. The underbody protective covering according to claim 117 of the patent application contains a dry inorganic pigment in a portion between 1% and 20%. The underbody protective covering of claim 117, which contains a dry inorganic pigment in a portion between 5% and 15%. A paint formulation characterized in that the formulation is contained according to an application A dry inorganic pigment according to any one of claims 1 to 25 and 83 to 87. A thick coating composition which is characterized by containing a dry inorganic pigment according to any one of claims 1 to 25 and 83 to 87. A coating formulation characterized by containing the dry inorganic pigment according to any one of claims 1 to 25 and 83 to 87. A paint formulation, characterized in that the formulation contains an aqueous suspension of an inorganic pigment according to any one of claims 88 to 102. A thick coating formulation which is characterized in that it contains an aqueous suspension of an inorganic pigment according to any one of claims 88 to 102. A coating formulation, characterized in that the formulation contains an aqueous suspension of an inorganic pigment according to any one of claims 88 to 102.